Chiral 2-(benzylsulfinyl)thiazole derivatives and 2-[(1H-pyrazol-4-ylmethyl)sulfinyl]thiazole derivatives, processes for their preparation and their use as herbicides and plant growth regulators

- Bayer Cropscience AG

The present invention provides chiral 2-(benzylsulfinyl)thiazole derivatives and 2-[(1H-pyrazol-4-ylmethyl)sulfinyl]thiazole derivatives of the formula (I) and their salts processes for their preparation and their use as herbicides and plant growth regulators, in particular as herbicides for the selective control of harmful plants in crops of useful plants.

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Description
CROSS REFERENCE TO RELATED APPLICATIONS

This application is a §371 national stage application of PCT/EP2008/009437 filed Nov. 8, 2008, which claims priority to European Application EP 07023198.0 filed Nov. 30, 2007.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to 2-(benzylsulfinyl)thiazole derivatives and 2-[(1H-pyrazol-4-ylmethyl)sulfinyl]thiazole derivatives. The present invention furthermore provides mixtures of the thiazole derivatives mentioned above with other herbicides and/or safeners. In addition, the present invention relates to processes for preparing the thiazole derivatives mentioned above and to the use of these compounds as plant growth regulators alone and in combination with safeners and/or in mixtures with other herbicides, in particular to their use for controlling plants in specific crop plants or as crop protection regulators.

2. Description of Related Art

It is already known from the prior art that certain 2-(benzylsulfinyl)thiazole derivatives and 2-[(1H-pyrazol-4-ylmethyl)sulfinyl]thiazole derivatives have herbicidal properties. Thus the Japanese patent application JP 2003/096059 describes herbicidally active thiazole derivatives which carry a benzylthio or benzylsulfonyl group as substituents at the 2-position of the thiazole ring.

WO 2006/123088 describes various 2-[(pyrazolylmethyl)thio]-, 2-[(pyrazolylmethyl)sulfinyl]- and 2-[(pyrazolylmethyl)sulfonyl]thiazole derivatives, their preparation and their use as herbicides.

However, on application, the active compounds already known from the publications mentioned above have disadvantages, be it

  • (a) that they have no or else insufficient herbicidal activity against harmful plants,
  • (b) that the spectrum of harmful plants that can be controlled with an active compound is not wide enough, or
  • (c) that their selectivity in crops of useful plants is insufficient.

In particular, the herbicidally active thiazole compounds known from the prior art have unsatisfactory herbicidal activity against certain weed grasses and at the same time unsatisfactory crop plant compatibility in certain crops.

SUMMARY OF THE INVENTION

It is therefore desirable to provide alternative chemical active compounds based on thiazole derivatives which can be used as herbicides or plant growth regulators and which are associated with certain advantages compared to systems known from the prior art.

It is thus the general object of the present invention to provide alternative thiazole derivatives which can be used as herbicides or plant growth regulators, in particular those having a satisfactory herbicidal action against harmful plants, covering a broad spectrum of harmful plants and/or having high selectivity in crops of useful plants. Preferably, these thiazole derivatives should have a better property profile, in particular better herbicidal activity against harmful plants, cover a broader spectrum of harmful plants and/or have higher selectivity in crops of useful plants than the thiazole derivatives known from the prior art.

A particular object of the present invention is to provide herbicidally active thiazole compounds having improved herbicidal activity against weed grasses compared to thiazole derivatives known from the prior art.

Another particular object of the present invention is to provide herbicidally active thiazole compounds having improved compatibility in specific crops compared to thiazole derivatives known from the prior art.

A particular object of the present invention is to provide herbicidally active thiazole compounds which, at the same time, have improved herbicidal activity against certain weed grasses and improved compatibility in specific crops compared to thiazole derivatives known from the prior art.

The present invention now provides specific 2-(benzylsulfinyl)thiazole derivatives and 2-[(1H-pyrazol-4-ylmethyl)sulfinyl]thiazole derivatives optically active at the sulfoxide function, which compounds have advantages compared to the compounds known from the prior art or racemic mixtures thereof.

According to the invention, it has been found that these inventive 2-(benzylsulfinyl)thiazole derivatives and 2-[(1H-pyrazol-4-ylmethyl)sulfinyl]thiazole derivatives optically active at the sulfoxide function have improved herbicidal activity against certain weed grasses compared to thiazole derivatives known from the prior art.

According to the invention, it has furthermore been found that these inventive 2-(benzylsulfinyl)thiazole derivatives and 2-[(1H-pyrazol-4-ylmethyl)sulfinyl]thiazole derivatives optically active at the sulfoxide function have improved crop plant compatibility in specific crops compared to thiazole derivatives known from the prior art.

Accordingly, the present invention provides optically active compounds of the formula (I), their agrochemically acceptable salts and their agrochemically acceptable quaternized nitrogen derivatives


in which

  • Y is either


and

    • the substituents R1 to R8 are each independently of one another selected from the group consisting of
      • hydrogen, halogen, hydroxyl, cyano, nitro, amino, C(O)OH, formyl,
      • (C1-C6)-alkyl, (C1-C6)-haloalkyl, (C1-C6)-alkylcarbonyl, (C1-C6)-haloalkylcarbonyl, (C1-C6)-alkylcarbonyloxy, (C1-C6)-haloalkylcarbonyloxy, (C1-C6)-alkylcarbonyl-(C1-C4)-alkyl, (C1-C6)-haloalkylcarbonyl-(C1-C4)-alkyl, (C1-C6)-alkylcarbonyl-(C1-C4)-haloalkyl, (C1-C6)-haloalkylcarbonyl-(C1-C4)-haloalkyl,
      • (C1-C6)-alkoxy, (C1-C6)-haloalkoxy, (C1-C6)-alkoxycarbonyl, (C1-C6)-haloalkoxycarbonyl, (C1-C6)-alkoxycarbonyl-(C1-C6)-alkyl, (C1-C6)-haloalkoxycarbonyl-(C1-C6)-alkyl, (C1-C6)-alkoxycarbonyl-(C1-C6)-haloalkyl, (C1-C6)-haloalkoxycarbonyl-(C1-C6)-haloalkyl,
      • (C2-C6)-alkenyl, (C2-C6)-haloalkenyl, (C2-C6)-alkenylcarbonyl, (C2-C6)-haloalkenylcarbonyl, (C2-C6)-alkenyloxy, (C2-C6)-haloalkenyloxy, (C2-C6)-alkenyloxycarbonyl, (C2-C6)-haloalkenyloxycarbonyl,
      • (C2-C6)-alkynyl, (C2-C6)-haloalkynyl, (C2-C6)-alkynylcarbonyl, (C2-C6)-haloalkynylcarbonyl, (C2-C6)-alkynyloxy, (C2-C6)-haloalkynyloxy, (C2-C6)-alkynyloxycarbonyl, (C2-C6)-haloalkynyloxycarbonyl,
      • (C1-C6)-alkylthiocarbonyl, (C1-C6)-haloalkylthiocarbonyl, (C1-C6)-alkylthiocarbonyloxy, (C1-C6)-haloalkylthiocarbonyloxy,
      • (C1-C6)-alkylthio-(C1-C6)-alkoxy, (C1-C6)-alkylthio-(C1-C6)-alkylcarbonyl, (C1-C6)-alkylthio-(C1-C6)-alkylcarbonyloxy,
      • (C6-C14)-aryl, (C6-C14)-aryloxy, (C6-C14)-arylcarbonyl, (C6-C14)-aryloxycarbonyl,
      • (C6-C14)-aryl-(C1-C6)-alkyl, (C6-C14)-aryl-(C1-C6)-alkoxy, (C6-C14)-aryloxy-(C1-C6)-alkyl, (C6-C14)-aryl-(C1-C6)-alkyl-carbonyl, (C6-C14)-aryl-(C1-C6)-alkyl-carbonyloxy, (C6-C14)-aryl-(C1-C6)-alkoxycarbonyl, (C6-C14)-aryl-(C1-C6)-alkoxycarbonyloxy,
      • (C1-C6)-alkylsulfonyl, (C1-C6)-alkylthio, (C1-C6)-alkylsulfinyl, (C1-C6)-haloalkylsulfonyl, (C1-C6)-haloalkylthio, (C1-C6)-haloalkylsulfinyl, (C1-C6)-alkylsulfonyl-(C1-C6)-alkyl, (C1-C6)-alkylthio-(C1-C6)-alkyl, (C1-C6)-alkylsulfinyl-(C1-C6)-alkyl, (C1-C6)-haloalkylsulfonyl-(C1-C6)-alkyl, (C1-C6)-haloalkylthio-(C1-C6)-alkyl, (C1-C6)-haloalkylsulfinyl-(C1-C6)-alkyl, (C1-C6)-alkylsulfonyl-(C1-C6)-haloalkyl, (C1-C6)-alkylthio-(C1-C6)-haloalkyl, (C1-C6)-alkylsulfinyl-(C1-C6)-haloalkyl, (C1-C6)-haloalkylsulfonyl-(C1-C6)-haloalkyl, (C1-C6)-haloalkylthio-(C1-C6)-haloalkyl, (C1-C6)-haloalkylsulfinyl-(C1-C6)-haloalkyl, (C1-C6)-alkylsulfonyloxy, (C1-C6)-haloalkylsulfonyloxy,
      • (C4-C14)-arylsulfonyl, (C6-C14)-arylthio, (C6-C14)-arylsulfinyl,
      • mono-((C1-C6)-alkyl)-amino, mono-((C1-C6)-haloalkyl)-amino, di-((C1-C6)-alkyl)-amino, di-((C1-C6)-haloalkyl)-amino, ((C1-C6)-alkyl-(C1-C6)-haloalkyl)-amino, N-((C1-C6)-alkanoyl)-amino, N-((C1-C6)-haloalkanoyl)-amino, aminocarbonyl-(C1-C6)-alkyl, mono-(C1-C6)-alkylaminocarbonyl-(C1-C6)-alkyl, di-(C1-C6)-alkylaminocarbonyl-(C1-C6)-alkyl, mono-((C1-C6)-alkyl)-aminocarbonyl,
      • (C1-C6)-alkoxy-(C1-C6)-alkyl, (C1-C6)-alkoxy-(C1-C6)-alkoxy, (C1-C6)-alkoxycarbonyl-(C1-C6)-alkoxy,
      • (C3-C8)-cycloalkyl, (C3-C8)-cycloalkoxy, (C3-C8)-cycloalkyl-(C1-C6)-alkyl, (C3-C8)-cycloalkyl-(C1-C6)-haloalkyl, (C3-C8)-cycloalkyl-(C1-C6)-alkoxy, (C3-C8)-cycloalkyl-(C1-C6)-haloalkoxy, (C3-C8)-cycloalkylcarbonyl, (C3-C8)-cycloalkoxycarbonyl, (C3-C8)-cycloalkyl-(C1-C6)-alkylcarbonyl, (C3-C8)-cycloalkyl-(C1-C6)-haloalkylcarbonyl, (C3-C8)-cycloalkyl-(C1-C6)-alkoxycarbonyl, (C3-C8)-cycloalkyl-(C1-C6)-haloalkoxycarbonyl, (C3-C8)-cycloalkylcarbonyloxy, (C3-C8)-cycloalkoxycarbonyloxy, (C3-C8)-cycloalkyl-(C1-C6)-alkylcarbonyloxy, (C3-C8)-cycloalkyl-(C1-C6)-haloalkylcarbonyloxy, (C3-C8)-cycloalkyl-(C1-C6)-alkoxycarbonyloxy, (C3-C8)-cycloalkyl-(C1-C6)-haloalkoxycarbonyloxy,
      • (C3-C8)-cycloalkenyl, (C3-C8)-cycloalkenyloxy, (C3-C8)-cycloalkenyl-(C1-C6)-alkyl, (C3-C8)-cycloalkenyl-(C1-C6)-haloalkyl, (C3-C8)-cycloalkenyl-(C1-C6)-alkoxy, (C3-C8)-cycloalkenyl-(C1-C6)-haloalkoxy, (C3-C8)-cycloalkenylcarbonyl, (C3-C8)-cycloalkenyloxycarbonyl, (C3-C8)-cycloalkenyl-(C1-C6)-alkylcarbonyl, (C3-C8)-cycloalkenyl-(C1-C6)-haloalkylcarbonyl, (C3-C8)-cycloalkenyl-(C1-C6)-alkoxycarbonyl, (C3-C8)-cycloalkenyl-(C1-C6)-haloalkoxycarbonyl, (C3-C8)-cycloalkenylcarbonyloxy, (C3-C8)-cycloalkenyloxycarbonyloxy, (C3-C8)-cycloalkenyl-(C1-C6)-alkylcarbonyloxy, (C3-C8)-cycloalkenyl-(C1-C6)-haloalkylcarbonyloxy, (C3-C8)-cycloalkenyl-(C1-C6)-alkoxycarbonyloxy, (C3-C8)-cycloalkenyl-(C1-C6)-haloalkoxycarbonyloxy,
      • (C3-C8)-cycloalkylthio, (C3-C8)-alkenylthio, (C3-C8)-cycloalkenylthio, (C3-C6)-alkynylthio,
      • hydroxy-(C1-C6)-alkyl, hydroxy-(C1-C6)-alkoxy, cyano-(C1-C6)-alkoxy, cyano-(C1-C6)-alkyl,
      • 3-oxetanyloxy,
      • C(O)NR9R10 where R9 and R10 independently of one another are hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C1-C6)-haloalkyl, or where R9 and R10 together form a (C1-C6)-alkylene group which may contain one oxygen or sulfur atom or one or two amino or (C1-C6)-alkylamino groups, where the radicals mentioned may, if appropriate, be attached cyclically to one another, provided they are ortho to one another
        • and/or
        • two substituents ortho to one another together form a (C1-C6)-alkylene group which may contain one or more oxygen and/or sulfur atoms, where the (C1-C6)-alkylene group may be mono- or polysubstituted by halogen and the halogen substituents in question may be identical or different; and
    • the substituents R11 and R12, in each case independently of one another, are selected from the group consisting of
      • hydrogen, halogen, nitro, cyano, formyl, C(O)OH, hydroxyl, amino,
      • (C1-C6)-alkyl, (C1-C6)-alkylcarbonyl, (C1-C6)-alkylcarbonyl-(C1-C4)-alkyl, (C1-C6)-alkylcarbonyloxy,
      • (C1-C6)-alkoxy, (C1-C6)-alkoxycarbonyl, (C1-C6)-alkoxycarbonyl-(C1-C6)-alkyl, (C1-C6)-alkoxy-(C1-C6)-alkyl, (C1-C6)-alkoxy-(C1-C6)-alkoxy, (C1-C6)-alkoxycarbonyl-(C1-C6)-alkoxy,
      • (C2-C6)-alkenyl, (C2-C6)-alkenyloxy, (C2-C6)-alkynyl, (C2-C6)-alkynyloxy,
      • (C1-C6)-alkylthio, (C1-C6)-alkylsulfinyl, (C1-C6)-alkylsulfonyl, (C1-C6)-alkylsulfonyloxy, (C1-C6)-alkylsulfonyl-(C1-C6)-alkyl, (C1-C6)-alkylsulfinyl-(C1-C6)-alkyl, (C1-C6)-alkylthio-(C1-C6)-alkyl, (C1-C6)-alkylthio-(C1-C6)-alkoxy,
      • mono-((C1-C6)-alkyl)-amino, di-((C1-C6)-alkyl)-amino, N-((C1-C6)-alkanoyl)-amino, aminocarbonyl-(C1-C6)-alkyl, mono-((C1-C6)-alkyl)-aminocarbonyl, di-((C1-C6)-alkyl)-aminocarbonyl, mono-((C1-C6)-alkyl)-aminosulfonyl, di-((C1-C6)-alkyl)-aminosulfonyl,
      • (C3-C8)-cycloalkyl, (C3-C8)-cycloalkoxy, (C3-C8)-cycloalkyl-(C1-C6)-alkyl, (C3-C8)-cycloalkyl-(C1-C6)-alkoxy, (C3-C8)-cycloalkylcarbonyl, (C3-C8)-cycloalkoxycarbonyl,
      • (C3-C8)-cycloalkenyl, (C3-C8)-cycloalkenyloxy, (C3-C8)-cycloalkylthio, (C3-C8)-cycloalkylsulfinyl, (C3-C8)-cycloalkylsulfonyl, (C3-C8)-cycloalkylsulfonyloxy,
      • cyano-(C1-C6)-alkoxy, cyano-(C1-C6)-alkyl,
      • (C6-C14)-aryl, (C6-C14)-aryloxy, (C6-C14)-aryl-(C1-C6)-alkyl, (C6-C14)-aryl-(C1-C6)-alkoxy, (C6-C14)-aryloxy-(C1-C6)-alkyl,
      • CONH—SO2—(C1-C6)-alkyl, —NHCHO, —NHCO—(C1-C6)-alkyl, —NHCO2—(C1-C6)-alkyl, —NHCONH—(C1-C6)-alkyl, —NHSO2—(C1-C6)-alkyl, —OCONH—(C1-C6)-alkyl, (C1-C6)-alkylaminosulfonyl-(C1-C2)-alkyl, di-(C1-C6)-alkylaminosulfonyl-(C1-C2)-alkyl, —C(O)NHR9, —C(O)NR9R10, where R9 and R10 independently of one another are hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C1-C6)-haloalkyl, or where R9 and R10 together form a (C1-C6)-alkylene group which may contain one oxygen or sulfur atom or one or two amino or (C1-C6)-alkylamino groups,
    • where the radicals R11 and R12 mentioned above may be mono-or polysubstituted independently of one another by radicals selected from the group consisting of halogen and (C1-C6)-alkyl; and
    • where the radicals cycloalkyl and aryl may be mono- or polysubstituted independently of one another.

If the radicals comprising cycloalkyl and aryl are substituted, the substituents are preferably selected from the group consisting of (C1-C6)-alkyl, (C1-C6)-haloalkyl, (C1-C6)-alkoxy, nitro, cyano, (C1-C3)-cycloalkyl, (C1-C6)-haloalkoxy, (C1-C6)-alkylthio, (C1-C6)-alkylcarbonyl, (C1-C6)-alkoxycarbonyl and halogen, where the radicals mentioned may, if appropriate, be cyclically attached to one another, provided they are ortho to each other.

DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT

A first embodiment of the present invention comprises compounds of the formula (I) in which

  • Y is


and

  • R1 is preferably selected from the group consisting of hydrogen, hydroxyl, halogen, cyano, nitro, amino, C(O)OH, (C1-C4)-alkyl, (C3-C6)-cycloalkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C1-C4)-alkoxy-(C1-C2)-alkyl, (C1-C3)-alkylcarbonyl, (C1-C3)-alkylcarbonyloxy, (C1-C4)-alkoxycarbonyl, (C3-C6)-cycloalkoxycarbonyl, (C3-C6)-cycloalkyl-(C1-C2)-alkoxy, (C3-C6)-cycloalkoxy, (C1-C4)-alkoxycarbonyl-(C1-C2)-alkoxy, (C3-C4)-alkenyloxy, (C3-C4)-alkynyloxy, (C1-C4)-alkylthio, (C1-C4)-haloalkylthio, (C1-C4)-alkylsulfinyl, (C1-C4)-haloalkylsulfinyl, (C1-C4)-alkylsulfonyl, (C1-C4)-haloalkylsulfonyl, (C1-C4)-alkylsulfonyloxy, di-(C1-C4)-alkylamino, C6-aryl-(C1-C4)-alkyl, (C3-C4)-alkenyloxycarbonyl, (C2-C4)-alkynyloxycarbonyl, C6-aryl-(C1-C4)-alkoxycarbonyl, C6-aryl-(C1-C4)-alkoxy, formyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, phenyl, —C(O)NR9R10, where R9 and R10 independently of one another are selected from the group consisting of hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C1-C6)-haloalkyl, or where R9 and R10 together form a (C1-C6)-alkylene group which may contain one oxygen or sulfur atom or one or two amino or (C1-C6)-alkylamino groups;
  • R1 is particularly preferably selected from the group consisting of H, F, Cl, Br, I, CN, OH, NH2, NO2, Me, Et, Ph, CHF2, CF3, OMe, OEt, OPr, OiPr, OBu, OcPen, OcHex, OCHF2, OCF3, OCH2CF3, C(O)OH, C(O)OMe, C(O)OEt, C(O)OPr, C(O)OiPr, C(O)OBu, C(O)OiBu, C(O)OsBu, C(O)OcPen, C(O)OCH2CH═CH2, C(O)OCH2C≡CH, C(O)OCH2Ph, CH2OMe, CH2OEt, CH2OBu, OCH2cPr, OCH2CH═CH2, OCH2C≡CH, OCH2Ph, OCH2C(O)OMe, OCH2C(O)OEt, OCH2CH2C(O)OMe, OCH2CH2C(O)OEt, OC(O)Me, OSO2Me, S(O)Me, SCF3, S(O)CF3 and S(O)2CF3;
  • R1 is very particularly preferably selected from the group consisting of H, F, Cl, Br, Me, CHF2, CF3, OMe, OCHF2, OCF3, OCH2CF3, I and OEt.

A second embodiment of the present invention comprises compounds of the formula (I) in which

  • Y is


and

  • R2 is preferably selected from the group consisting of hydrogen, hydroxyl, halogen, cyano, nitro, amino, C(O)OH, (C1-C4)-alkyl, (C3-C6)-cycloalkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C1-C4)-alkoxy-(C1-C2)-alkyl, (C1-C3)-alkylcarbonyl, (C1-C3)-alkylcarbonyloxy, (C1-C4)-alkoxycarbonyl, (C3-C6)-cycloalkoxycarbonyl, (C3-C6)-cycloalkyl-(C1-C2)-alkoxy, (C3-C6)-cycloalkoxy, (C1-C4)-alkoxycarbonyl-(C1-C2)-alkoxy, (C3-C4)-alkenyloxy, (C3-C4)-alkynyloxy, (C1-C4)-alkylthio, (C1-C4)-haloalkylthio, (C1-C4)-alkylsulfinyl, (C1-C4)-haloalkylsulfinyl, (C1-C4)-alkylsulfonyl, (C1-C4)-haloalkylsulfonyl, (C1-C4)-alkylsulfonyloxy, di-(C1-C4)-alkylamino, C6-aryl-(C1-C4)-alkyl, (C3-C4)-alkenyloxycarbonyl, (C2-C4)-alkynyloxycarbonyl, C6-aryl-(C1-C4)-alkoxycarbonyl, C6-aryl-(C1-C4)-alkoxy, formyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, phenyl, —C(O)NR9R10, where R9 and R10 independently of one another are selected from the group consisting of hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C1-C6)-haloalkyl, or where R9 and R10 together form a (C1-C6)-alkylene group which may contain one oxygen or sulfur atom or one or two amino or (C1-C6)-alkylamino groups;
  • R2 is particularly preferably selected from the group consisting of H, F, Cl, Br, OH, NO2, Me, iPr, CHF2, CF3, OMe, OEt, OPr, OiPr, OBu, OCHF2, OCF3, OCH2CF3, C(O)OH and C(O)OMe;
  • R2 is very particularly preferably selected from the group consisting of H, F, Cl, Me, CF3 and OMe.

A third embodiment of the present invention comprises compounds of the formula (I) in which

  • Y is


and

  • R3 is preferably selected from the group consisting of hydrogen, hydroxyl, halogen, cyano, nitro, amino, C(O)OH, (C1-C4)-alkyl, (C3-C6)-cycloalkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C1-C4)-alkoxy-(C1-C2)-alkyl, (C1-C3)-alkylcarbonyl, (C1-C3)-alkylcarbonyloxy, (C1-C4)-alkoxycarbonyl, (C3-C6)-cycloalkoxycarbonyl, (C3-C6)-cycloalkyl-(C1-C2)-alkoxy, (C3-C6)-cycloalkoxy, (C1-C4)-alkoxycarbonyl-(C1-C2)-alkoxy, (C3-C4)-alkenyloxy, (C3-C4)-alkynyloxy, (C1-C4)-alkylthio, (C1-C4)-haloalkylthio, (C1-C4)-alkylsulfinyl, (C1-C4)-haloalkylsulfinyl, (C1-C4)-alkylsulfonyl, (C1-C4)-haloalkylsulfonyl, (C1-C4)-alkylsulfonyloxy, di-(C1-C4)-alkylamino, C6-aryl-(C1-C4)-alkyl, (C3-C4)-alkenyloxycarbonyl, (C2-C4)-alkynyloxycarbonyl, C6-aryl-(C1-C4)-alkoxycarbonyl, C6-aryl-(C1-C4)-alkoxy, formyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, phenyl, —C(O)NR9R10, where R9 and R10 independently of one another are selected from the group consisting of hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C1-C6)-haloalkyl, or where R9 and R10 together form a (C1-C6)-alkylene group which may contain one oxygen or sulfur atom or one or two amino or (C1-C6)-alkylamino groups;
  • R3 is particularly preferably selected from the group consisting of H, F, Cl, Br, OH, Me, CF3, OMe, OCHF2, OCF3, OCH2CF3, C(O)OMe and C(O)OEt; and
  • R3 is very particularly preferably selected from the group consisting of H, F, Cl, Br, CF3 and Me.

A fourth embodiment of the present invention comprises compounds of the formula (I) in which

  • Y is


and

  • R4 is preferably selected from the group consisting of hydrogen, hydroxyl, halogen, cyano, nitro, amino, C(O)OH, (C1-C4)-alkyl, (C3-C6)-cycloalkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C1-C4)-alkoxy-(C1-C2)-alkyl, (C1-C3)-alkylcarbonyl, (C1-C3)-alkylcarbonyloxy, (C1-C4)-alkoxycarbonyl, (C3-C6)-cycloalkoxycarbonyl, (C3-C6)-cycloalkyl-(C1-C2)-alkoxy, (C3-C6)-cycloalkoxy, (C1-C4)-alkoxycarbonyl-(C1-C2)-alkoxy, (C3-C4)-alkenyloxy, (C3-C4)-alkynyloxy, (C1-C4)-alkylthio, (C1-C4)-haloalkylthio, (C1-C4)-alkylsulfinyl, (C1-C4)-haloalkylsulfinyl, (C1-C4)-alkylsulfonyl, (C1-C4)-haloalkylsulfonyl, (C1-C4)-alkylsulfonyloxy, di-(C1-C4)-alkylamino, C6-aryl-(C1-C4)-alkyl, (C3-C4)-alkenyloxycarbonyl, (C2-C4)-alkynyloxycarbonyl, C6-aryl-(C1-C4)-alkoxycarbonyl, C6-aryl-(C1-C4)-alkoxy, formyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, phenyl, —C(O)NR9R10, where R9 and R10 independently of one another are selected from the group consisting of hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C1-C6)-haloalkyl, or where R9 and R10 together form a (C1-C6)-alkylene group which may contain one oxygen or sulfur atom or one or two amino or (C1-C6)-alkylamino groups;
  • R4 is particularly preferably selected from the group consisting of H, F, Cl, Br, NO2, Me, iPr, OMe, OEt, OPr, OiPr, OBu, OCHF2, CF3, OCF3, OCH2CF3, OCH2CH═CH2 and OCH2C≡CH; and
  • R4 is very particularly preferably selected from the group consisting of H, F, Cl, Me, CF3 and OMe.

A fifth embodiment of the present invention comprises compounds of the formula (I) in which

  • Y is


and

  • R5 is preferably selected from the group consisting of hydrogen, hydroxyl, halogen, cyano, nitro, amino, C(O)OH, (C1-C4)-alkyl, (C3-C6)-cycloalkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C1-C4)-alkoxy-(C1-C2)-alkyl, (C1-C3)-alkylcarbonyl, (C1-C3)-alkylcarbonyloxy, (C1-C4)-alkoxycarbonyl, (C3-C6)-cycloalkoxycarbonyl, (C3-C6)-cycloalkyl-(C1-C2)-alkoxy, (C3-C6)-cycloalkoxy, (C1-C4)-alkoxycarbonyl-(C1-C2)-alkoxy, (C3-C4)-alkenyloxy, (C3-C4)-alkynyloxy, (C1-C4)-alkylthio, (C1-C4)-haloalkylthio, (C1-C4)-alkylsulfinyl, (C1-C4)-haloalkylsulfinyl, (C1-C4)-alkylsulfonyl, (C1-C4)-haloalkylsulfonyl, (C1-C4)-alkylsulfonyloxy, di-(C1-C4)-alkylamino, C6-aryl-(C1-C4)-alkyl, (C3-C4)-alkenyloxycarbonyl, (C2-C4)-alkynyloxycarbonyl, C6-aryl-(C1-C4)-alkoxycarbonyl, C6-aryl-(C1-C4)-alkoxy, formyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, phenyl, —C(O)NR9R10, where R9 and R10 independently of one another are selected from the group consisting of hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C1-C6)-haloalkyl, or where R9 and R10 together form a (C1-C6)-alkylene group which may contain one oxygen or sulfur atom or one or two amino or (C1-C6)-alkylamino groups;
  • R5 is particularly preferably selected from the group consisting of H, F, Cl, Br, OH, NO2, NMe2, NEt2, Me, Et, CHF2, CF3, OMe, OEt, OPr, OiPr, OBu, OiBu, OCHF2, OCF3, OCH2CF3, C(O)OH, C(O)OMe, C(O)OEt, C(O)OPr, C(O)OiPr, C(O)OBu, C(O)OiBu, C(O)OsBu, C(O)OCH2Ph, OCH2CH═CH2 and OCH2C≡CH; and
  • R5 is very particularly preferably selected from the group consisting of H, F, Cl, Me, CF3, OCHF2, OCF3 and OMe.

In the context of the first to fifth embodiment of the present invention, it is possible to combine the specific preferred, particularly preferred and very particularly preferred meanings of the substituents R1 to R5 as desired. This means that the present invention comprises compounds of the formula (I) where Y is


in which, for example, the substituent R1 has a preferred meaning and the substituents R2 to R5 have the general meaning, or else, for example, the substituent R2 has a preferred meaning, the substituent R3 has a particularly preferred meaning, the substituent R4 has a very particular meaning and the substituents R1 and R5 have the general meaning.

A sixth embodiment of the present invention comprises compounds of the formula (I) in which

  • Y is


and

  • R6 is preferably selected from the group consisting of hydrogen, halogen, hydroxyl, cyano, nitro, amino, (C1-C4)-alkyl, (C3-C6)-cycloalkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-alkoxy-(C1-C2)-alkyl, (C3-C6)-cycloalkoxy, (C1-C4)-haloalkoxy, (C1-C4)-alkylthio, (C1-C4)-alkylthio-(C1-C2)-alkyl, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfinyl-(C1-C2)-alkyl, (C1-C4)-alkylsulfonyl, (C1-C4)-alkylsulfonyl-(C1-C2)-alkyl, di-(C1-C4)-alkylamino, (C2-C4)-alkenyl, (C2-C4)-alkynyl, (C3-C4)-alkenyloxy, (C3-C4)-alkynyloxy, (C3-C6)-cycloalkyl-(C1-C2)-alkoxy, hydroxy-(C1-C2)-alkyl, hydroxy-(C1-C2)-alkoxy, cyano-(C1-C2)-alkoxy, cyano-(C1-C2)-alkyl, phenyl, phenyl-(C1-C2)-alkyl, phenyl-(C1-C2)-alkoxy, phenoxy, (C1-C4)-alkylcarbonyloxy, (C3-C6)-cycloalkyl-(C1-C2)-alkyl, (C1-C4)-alkylcarbonyl-(C1-C2)-alkyl, (C1-C4)-alkoxycarbonyl-(C1-C2)-alkyl, aminocarbonyl-(C1-C2)-alkyl and 3-oxetanyloxy, —C(O)NR9R10, where R9 and R10 independently of one another are selected from the group consisting of hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C1-C6)-haloalkyl, or where R9 and R10 together form a (C1-C6)-alkylene group which may contain one oxygen or sulfur atom or one or two amino or (C1-C6)-alkylamino groups; and
  • R6 is particularly preferably selected from the group consisting of H, F, Cl, Br, I, CN, Me, Et, Pr, iPr, tBu, CHF2, CF3, OMe, OEt, OCHF2 and OCH2CF3; and
  • R6 is very particularly preferably selected from the group consisting of F, Cl, Br, CHF2, CF3, OCHF2, OCF3, OCH2CF3, Me, OMe and Et.

A seventh embodiment of the present invention comprises compounds of the formula (I) in which

  • Y is


and

  • R7 is preferably selected from the group consisting of hydrogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl, phenyl, phenyl-(C1-C2)-alkyl, (C3-C6)-cycloalkyl; (C3-C6)-cycloalkyl-(C1-C2)-alkyl, where the cycloalkyl radical is optionally substituted by (C1-C4)-alkyl; (C2-C4)-alkenyl, (C2-C4)-alkynyl, (C1-C4)-alkoxy-(C1-C2)-alkyl, (C1-C4)-alkylthio-(C1-C2)-alkyl, (C1-C4)-alkylsulfinyl-(C1-C2)-alkyl, cyano-(C1-C2)-alkyl, (C1-C4)-alkylsulfonyl-(C1-C2)-alkyl, (C1-C4)-alkoxycarbonyl-(C1-C2)-alkyl, aminocarbonyl-(C1-C2)-alkyl, mono-(C1-C4)-alkylaminocarbonyl-(C1-C2)-alkyl, di-(C1-C4)-alkylaminocarbonyl-(C1-C2)-alkyl, hydroxy-(C1-C4)-alkyl, (C1-C4)-alkylcarbonyl-(C1-C4)-alkyl, (C1-C4)-alkoxycarbonyl-(C1-C2)-alkyl, (C1-C4)-alkylsulfonyl; phenylsulfonyl which is optionally substituted by one or more identical or different radicals from the group consisting of halogen, nitro, cyano, (C1-C6)-alkyl, (C1-C6)-haloalkyl, (C3-C6)-cycloalkyl, (C1-C6)-alkoxy, (C1-C6)-haloalkoxy and (C1-C6)-alkylthio; (C1-C4)-alkylcarbonyl; phenylcarbonyl which is optionally substituted by one or more identical or different radicals from the group consisting of halogen, nitro, cyano, (C1-C6)-alkyl, (C1-C6)-haloalkyl, (C3-C6)-cycloalkyl, (C1-C6)-alkoxy, (C1-C6)-haloalkoxy and (C1-C6)-alkylthio; and (C1-C4)-alkoxycarbonyl;
  • R7 is particularly preferably selected from the group consisting of H, Me, Et, Pr, cPr, iPr, Bu, iBu, sBu, tBu, cPen, cHex, CHF2, CH2CF3, Ph, Ph(4-Cl), CH2cPr, CH2cPr(2-Me), CHMecPr, CH2cBu, CH2cPen, CH2cHex, CH2Ph, CH2CH═CH2, CH2C≡CH, CHMeC≡CH, CH2C≡CMe, CH2OMe, CH2OEt, CH2CH2OH, CH2CH2OMe, CH2CH2OEt, CH2CH2C(O)Me, CH2SMe, CH2SO2Me, CH2CN, CH2C(O)OMe, CH2C(O)OEt, CH2C(O)NH2, CH2C(O)NMe2, CH2C(O)Me, SO2Me, SO2Ph, C(O)Me, C(O)Ph and C(O)OMe; and
  • R7 is very particularly preferably selected from the group consisting of Me, Et and CHF2.

An eighth embodiment of the present invention comprises compounds of the formula (I) in which

  • Y is


and

  • R8 is preferably selected from the group consisting of hydrogen, halogen, hydroxyl, cyano, nitro, amino, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C3-C6)-cycloalkyl, (C1-C4)-alkoxy, (C1-C4)-alkoxy-(C1-C4)-alkoxy, (C1-C4)-alkoxy-(C1-C2)-alkyl, (C3-C6)-cycloalkoxy, (C1-C4)-haloalkoxy, (C1-C4)-alkylthio, (C1-C4)-alkylthio-(C1-C2)-alkyl, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfinyl-(C1-C2)-alkyl, (C1-C4)-alkylsulfonyl, (C1-C4)-alkylsulfonyl-(C1-C2)-alkyl, di-(C1-C4)-alkylamino, (C2-C4)-alkenyl, (C2-C4)-haloalkenyl, cyano-(C1-C4)-alkyl, (C2-C4)-alkynyl, (C3-C4)-alkenyloxy, (C3-C4)-alkynyloxy, (C3-C6)-cycloalkyl-(C1-C2)-alkoxy, hydroxy-(C1-C2)-alkyl, hydroxy-(C1-C2)-alkoxy, cyano-(C1-C2)-alkoxy, cyano-(C1-C2)-alkyl, phenyl, phenyl-(C1-C2)-alkyl, phenyl-(C1-C2)-alkoxy, phenoxy, (C1-C4)-alkylcarbonyloxy, (C3-C6)-cycloalkyl-(C1-C2)-alkyl, (C1-C4)-alkylcarbonyl-(C1-C2)-alkyl, (C1-C4)-alkoxycarbonyl-(C1-C2)-alkyl, aminocarbonyl-(C1-C2)-alkyl and 3-oxetanyloxy, —C(O)NR9R10, where R9 and R10 independently of one another are selected from the group consisting of hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C1-C6)-haloalkyl, or where R9 and R10 together form a (C1-C6)-alkylene group which may contain one oxygen or sulfur atom or one or two amino or (C1-C6)-alkylamino groups; and
  • R8 is particularly preferably selected from the group consisting of H, F, Cl, Br, I, CN, Me, Et, CHF2, CF3, OCHF2, OCH2CF3, OMe, OEt, OPr, OiPr, OtBu, SO2Me, SO2iPr, 3-Oxetanyloxy-, OPh, OCH2CH═CH2, OCH2C≡CH, OCH2CHF2, SEt, OCH2CH2OCH3, SMe, OCH2CH2CH2F, OCH(CH2F)2, OCH2CF═CH2, OCH(CH3)CF3, OCH2CN, OCH(CH3)CH2F, OCH2CF2CHF2 and OCH(CH3)2; and
  • R8 is very particularly preferably selected from the group consisting of F, Cl, Br, CHF2, CF3, OCHF2 and OCH2CF3.

In the context of the sixth to eighth embodiments of the present invention, it is possible to combine the individual preferred, particularly preferred and very particularly preferred meanings of the substituents R6 to R8. This means that the present invention comprises compounds of the formula (I) where Y is


in which, for example, the substituent R6 has a preferred meaning and the substituents R7 and R8 have the general meaning, or else the substituent R7 has a preferred meaning, the substituent R8 has a particularly preferred meaning and the substituent R6 has a very particularly preferred meaning.

The preferred, particularly preferred and very particularly preferred definitions of the radicals R1 to R8 defined in these embodiments of the present invention can be combined in any combination with the meanings of the substituents R11 and R12 defined hereinbelow as preferred.

Accordingly, preferred, particularly preferred and very particularly preferred meanings of the radicals R are as follows:

Preferred meanings of the radicals R11 and R12 can be selected independently of one another from the group consisting of

    • H, halogen, nitro, cyano, carboxyl, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C3-C6)-cycloalkoxy, (C1-C6)-alkoxy, (C1-C6)-alkylcarbonyl, (C3-C6)-cycloalkylcarbonyl, (C1-C6)-alkoxycarbonyl, (C3-C6)-cycloalkoxycarbonyl, mono-((C1-C4)-alkyl)-aminocarbonyl, di-((C1-C4)-alkyl)-aminocarbonyl, mono-((C1-C4)-alkyl)-aminosulfonyl, di-((C1-C4)-alkyl)-aminosulfonyl, (C1-C4)-alkylthio, (C3-C6)-cycloalkylthio, (C1-C4)-alkylsulfinyl, (C3-C6)-cycloalkylsulfinyl, (C1-C4)-alkylsulfonyl, (C3-C6)-cycloalkylsulfonyl, (C1-C4)-alkylsulfonyloxy, (C3-C6)-cycloalkylsulfonyloxy, (C2-C3)-alkenyl, (C2-C3)-alkynyl, (C2-C3)-alkenyloxy, (C2-C3)-alkynyloxy, —NHCO—(C1-C3)-alkyl, —NHCO2—(C1-C3)-alkyl, —NHCONH—(C1-C3)-alkyl, —NHSO2—(C1-C3)-alkyl, —OCONH—(C1-C3)-alkyl, —CONHR9, —CONR9R10,
      • where R9 and R10 independently of one another are hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C1-C6)-haloalkyl,
      • where the radicals R11 and R12 mentioned above may be mono- or polysubstituted independently of one another by radicals selected from the group consisting of halogen and (C1-C6)-alkyl.

Particularly preferred meanings of the radicals R11 and R12 can be selected independently of one another from the group consisting of H, F, Cl, Br, I, Me, Et, NO2, C(O)OEt, CHF2 and CF3.

Very particularly preferred meanings of the radicals R11 and R12 can be selected independently of one another from the group consisting of H, F, Cl, Br, I, Me, CHF2, NO2 and CF3, with F, Cl, Br and I being most preferred.

In the context of the present invention, the compounds of the formula (I) also comprise compounds quaternized at a nitrogen atom by a) protonation, b) alkylation or c) oxidation.

In addition, the present invention also provides compounds of the formula (Ic) in racemic form


in which Y corresponds to


and the radicals R1 to R5 and R11 and R12 have the above general, preferred, particularly preferred and very particularly preferred meanings, except for the compound 2-benzylsulfinylthiazole and the compounds 2-(benzylsulfinyl)-1,3-thiazole, 2-(benzylsulfinyl)-5-(chloromethyl)-1,3-thiazole, 5-(chloromethyl)-2-[(4-methylbenzyl)sulfinyl]-1,3-thiazole, 5-(chloromethyl)-2-[(4-methoxybenzyl)sulfinyl]-1,3-thiazole, 2-[(4-chlorobenzyl)sulfinyl]-5-(chloromethyl)-1,3-thiazole, 5-(chloromethyl)-2-[(4-nitrobenzyl)sulfinyl]-1,3-thiazole, 5-(bromomethyl)-2-[(4-nitrobenzyl)sulfinyl]-1,3-thiazole, 5-(bromomethyl)-2-[(4-chlorobenzyl)sulfinyl]-1,3-thiazole, 5-(bromomethyl)-2-[(4-methoxybenzyl)sulfinyl]-1,3-thiazole, 5-(bromomethyl)-2-[(4-methylbenzyl)sulfinyl]-1,3-thiazole, 2-(benzylsulfinyl)-5-(bromomethyl)-1,3-thiazole.

Except for the compound 2-benzylsulfinylthiazole (J. Heterocyclic Chem. 1978, 15(8), 1361), corresponding compounds of the formula (Ic) are not known. J. Heterocyclic Chem. 1978, 15(8), 1361 does not disclose any information as to the herbicidal action of corresponding compounds.

If appropriate, the compounds of the formula (I) may be able to form salts by forming an adduct with a suitable inorganic or organic acid, such as, for example, HCl, HBr, H2SO4 or HNO3, or else oxalic acid or sulfonic acids, to a basic group, such as, for example, amino or alkylamino. Suitable substituents present in deprotonated form, such as, for example, sulfonic acids or carboxylic acids, are capable of forming inner salts with groups, such as amino groups, which for their part can be protonated. Salts can also be formed by replacing the hydrogen of suitable substituents, such as, for example, sulfonic acids or carboxylic acids, with a cation suitable in the agrochemical sector. These salts are, for example, metal salts, in particular alkali metal salts or alkaline earth metal salts, especially sodium salts or potassium salts, or else ammonium salts, salts with organic amines or quaternary ammonium salts having cations of the formula [NRR′R″R′″]+ in which R to R′″ in each case independently denote an organic radical, in particular alkyl, aryl, aralkyl or alkylaryl.

In the formula (I) and in all the other formulae of the present invention, the radicals alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino, alkylthio, haloalkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylsulfinyl and haloalkylsulfonyl and the corresponding unsaturated and/or substituted radicals can in each case be straight-chain or branched in the carbon skeleton. Unless indicated specifically, preference is given for these radicals to the lower carbon skeletons, for example those having 1 to 6 carbon atoms, especially 1 to 4 carbon atoms, or in the case of unsaturated groups having 2 to 6 carbon atoms, especially 2 to 4 carbon atoms. Alkyl radicals, also in composite definitions such as alkoxy, haloalkyl, etc., are for example methyl, ethyl, propyls, such as n-propyl or isopropyl, butyls, such as n-butyl, isobutyl or tert-butyl, pentyls, such as n-pentyl, isopentyl or neopentyl, hexyls, such as n-hexyl, isohexyl, 3-methylpentyl, 2,2-dimethylbutyl or 2,3-dimethylbutyl, heptyls, such as n-heptyl, 1-methylhexyl or 1,4-dimethylpentyl; alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals; where at least one double bond or triple bond is present, preferably one double bond or triple bond, respectively. Alkenyl is, for example, vinyl, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methylbut-3-en-1-yl, and 1-methylbut-2-en-1-yl; alkynyl is, for example, ethynyl, propargyl, but-2-yn-1-yl, but-3-yn-1-yl and 1-methylbut-3-yn-1-yl.

Cycloalkyl groups are, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. The cycloalkyl groups can be present in bi- or tricyclic form.

If haloalkyl groups and haloalkyl radicals of haloalkoxy, haloalkylthio, haloalkenyl, haloalkynyl etc. are stated, the lower carbon skeletons of these radicals having, for example, 1 to 6 carbon atoms or 2 to 6 carbon atoms, in particular 1 to 4 carbon atoms or preferably 2 to 4 carbon atoms, and the corresponding unsaturated and/or substituted radicals are in each case straight-chain or branched in the carbon skeleton. Examples are difluoromethyl, 2,2,2-trifluoroethyl, trifluoroallyl, 1-chloroprop-1-yl-3-yl. According to the invention, the term “halo” is used synonymously with “halogen”.

Alkylene groups in these radicals are the lower carbon skeletons, for example those having 1 to 10 carbon atoms, in particular 1 to 6 carbon atoms, or preferably 2 to 4 carbon atoms (unless defined otherwise), and also the corresponding unsaturated and/or substituted radicals in the carbon skeleton which may in each case be straight-chain or branched. Examples are methylene, ethylene, n- and isopropylene and n-, s-, iso-, t-butylene.

Hydroxyalkyl groups in these radicals are the lower carbon skeletons, for example those having 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms, and also the corresponding unsaturated and/or substituted radicals in the carbon skeleton which may in each case be straight-chain or branched. Examples of these are 1,2-dihydroxyethyl and 3-hydroxypropyl.

Halogen is fluorine, chlorine, bromine or iodine. Haloalkyl, haloalkenyl and haloalkynyl are alkyl, alkenyl or alkynyl, respectively, which are fully or partly substituted by halogen, preferably by fluorine, chlorine or bromine, in particular by fluorine and/or chlorine, examples being monohaloalkyl (i.e., monohalogenalkyl), perhaloalkyl, CF3, CHF2, CH2F, CF3CF2, CH2FCHCl, CCl3, CHCl2, CH2CH2Cl; haloalkoxy is, for example, OCF3, OCHF2, OCH2F, CF3CF2O, OCH2CF3 and OCH2CH2Cl; this correspondingly applies to haloalkenyl and other halogen-substituted radicals.

Aryl is a monocyclic, bicyclic or polycyclic aromatic system, for example phenyl or naphthyl, preferably phenyl.

The definition “substituted by one or more radicals” refers, unless otherwise defined, to one or more identical or different radicals.

The substituents given by way of example (“first substituent level”) can, if they include hydrocarbon-containing fractions, be further substituted therein if desired (“second substituent level”), by for example one of the substituents as defined for the first substituent level. Corresponding further substituent levels are possible. The term “substituted radical” preferably embraces just one or two substituent levels.

In the case of radicals having carbon atoms, preference is given to those having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms. Preference is generally given to substituents from the group consisting of halogen, for example fluorine and chlorine, (C1-C4)-alkyl, preferably methyl or ethyl, (C1-C4)-haloalkyl, preferably trifluoromethyl, (C1-C4)-alkoxy, preferably methoxy or ethoxy, (C1-C4)-haloalkoxy, nitro and cyano.

If an aryl radical is substituted, it may preferably be phenyl which is mono- or polysubstituted, preferably up to trisubstituted, by identical or different radicals from the group consisting of halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkyl, (C1-C4)-haloalkoxy, cyano and nitro, for example o-, m- and p-tolyl, dimethylphenyls, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-trifluoromethyl and 2-, 3- and 4-trichloromethylphenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, o-, m- and p-methoxyphenyl.

Primarily for reasons of higher herbicidal activity, better selectivity and/or better producibility, compounds of the formula (I) according to the invention or their agrochemical salts or quaternary N derivatives are of particular interest in which individual radicals have one of the preferred meanings already specified or specified below, or in particular those in which one or more of the preferred meanings already specified or specified below occur in combination.

The abovementioned general or preferred radical definitions apply both to the end products of the formula (I) and, correspondingly, to the starting materials and the intermediates required in each case for the preparation. These radical definitions can be exchanged for one another as desired, i.e. including combinations between the given preferred ranges.

The present compounds of the formula (I) have a chiral sulfur atom which, in the structure shown above, is illustrated by the marker (*). According to the rules of Cahn, Ingold and Prelog (CIP rules), this sulfur atom can have either an (R) configuration or an (S) configuration.

The present invention encompasses compounds of the formula (I) both with (S) and with (R) configuration, i.e. the present invention encompasses the compounds of the formula (I) in which the sulfur atom in question has

  • (1) an (R) configuration; or
  • (2) an (S) configuration.

In addition, the scope of the present invention also encompasses

  • (3) any mixtures of compounds of the formula (I) having an (R) configuration (compounds of the formula (I-(R)) with compounds of the formula (I) having an (S) configuration (compounds of the formula (I-(S)),
    where a racemic mixture of the compounds of the formula (I) having (R) and (S) configuration is excluded from the present invention.

Within the context of the present invention, preference is given to using in particular compounds of the formula (I) having (S) configuration (compounds of the formula (I-S)) compared to the (R) configuration (compounds of the formula (I-R)) with a selectivity of 60 to 100%, preferably 80 to 100%, in particular 90 to 100%, very particularly preferably 95 to 100%, where the particular (S) compound is present with an enantioselectivity of in each case more than 50% ee, preferably 60 to 100% ee, in particular 80 to 100% ee, very particularly 90 to 100% ee, most preferably 95 to 100% ee, based on the total content of (S) compound in question.

Accordingly, the present invention relates in particular to compounds of the formula (I) in which the stereochemical configuration on the sulfur atom marked by (*) is present with a stereochemical purity of 60 to 100% (S), preferably 80 to 100% (S), in particular 90 to 100% (S), very particularly 95 to 100% (S).

Depending on the type and attachment of the substituents, the compounds of the formula (I) may contain further centers of chirality in addition to the sulfur atom marked (*) in formula (I), in which case they are then present as stereoisomers. In the context of the present invention, the definition of the formula (I) comprises all stereoisomers, such as enantiomers, diasteromers and Z and E isomers, defined by their specific spatial form, i.e. the present invention comprises both the pure stereoisomers and less pure mixtures thereof. Here, preference is given in particular to compounds which, at the sulfur atom marked (*), have a stereochemical purity of from 60 to 100% (S), preferably from 80 to 100% (S), in particular from 90 to 100% (S), very particularly from 95 to 100% (S), and, at the remaining stereocenters, are present in racemic form or in a more or less pronounced stereochemical purity.

If, for example, one or more alkenyl groups are present, there may be diastereomers (Z and E isomers).

If, for example, one or more asymmetric carbon atoms are present, there may be enantiomers and diastereomers.

Corresponding stereoisomers may be obtained from the mixtures resulting from the preparation using customary separation methods, for example by chromatographic separation techniques. It is also possible to prepare stereoisomers selectively by using stereoselective reactions employing optically active starting materials and/or auxiliaries. Accordingly, the invention also relates to all stereoisomers embraced by the formula (I) but not shown in their specific stereoform, and to their mixtures.

For the possible combinations of the various substituents of the formula (I) the general principles of the construction of chemical compounds have to be observed, i.e. the formula (I) does not comprise any compounds known to the person skilled in the art as being chemically impossible.

The present invention furthermore provides processes for preparing corresponding compounds of the formula (I) and/or salts thereof and/or agrochemically acceptable quaternized nitrogen derivatives thereof:

  • a.) To prepare optically active sulfoxides of the formula (I), for example, a thioether of the formula (II)

    • in which Y has the meanings given above for formula (I) is oxidized with one equivalent of an oxidizing agent to the sulfoxides (I):

    • The oxidizing agents which can be used for this reaction are not subject to any particular requirements, and it is possible to use any oxidizing agent capable of oxidizing the sulfur compounds in question to sulfoxide compounds. Oxidizing agents suitable for preparing the sulfoxides are inorganic peroxides, such as, for example, hydrogen peroxide, sodium metaperiodate, organic peroxides, such as, for example, tert-butyl hydroperoxide, or organic peracids, such as peracetic acid or, preferably, 3-chloroperbenzoic acid. The reaction can be carried out in halogenated hydrocarbons, for example dichloromethane, 1,2-dichloroethane, an alcohol, such as, for example, methanol, or in dimethylformamide, water or acetic acid, or in a mixture of the solvents mentioned above. The reaction can be carried out in a temperature range of between −80° C. and 120° C., preferably between −20° C. and 50° C. Such processes are known in the literature and are described, for example, in J. Org. Chem., 58 (1993) 2791, J. Org. Chem., 68 (2003) 3849 and J. Heterocyclic Chem., 15 (1978) 1361, the relevant disclosure of which is incorporated by reference into the present invention.
    • The preparation of the thioethers of the formula (II) is known, for example, from JP 2003/096059 and WO 2006/123088.
  • b) Compounds of the formula (I) can additionally be prepared by processes as described, for example, in JP 2003/096059 and WO 2006/123088, WO 2001/012613, WO 2002/062770, WO 2003/000686, WO 2003/010165, WO 2004/013106, WO 2006/024820, WO 2007/003294, WO 2007/003295.
  • c) The enantioselective synthesis of chiral sulfoxides of the formula (I) in optically enriched or pure form can be carried out from compounds of the general formula (II) using methods as described, for example, in Chem. Rev., 103 (2003) 3651-3705 and the literature cited therein, and Adv. Synth. Catal. 347 (2005) 19-31 and the literature cited therein. In each individual case, the absolute configuration of the product depends on the structure of the optically active catalyst.

Corresponding salts can be prepared in a manner known per se to the person skilled in the art.

Compounds of the formula (Ia)


consist of a mixture of the respective enantiomers (Ia-S) and (Ia-R) which are chiral at the sulfoxide function


where the radicals R1, R2, R3, R4, R5, R11 and R12 have the meanings given above for the formula (I).

Compounds of the formula (Ib)


consist of a mixture of the respective enantiomers (Ib-S) and (Ib-R) which are chiral at the sulfoxide function


where the radicals R6, R7, R8, R11 and R12 have the meanings given above for the formula (I).

Suitable for preparing enantiomers of the formula (I) are, in addition to enantioselective syntheses, also customary methods for the separation of racemates (cf. textbooks of stereochemistry).

Racemic mixtures, for example of optically active sulfoxides of the formula (I), can be separated by known processes. Such methods for the separation of racemates are described in handbooks of stereochemistry, for example in “Basic Organic Stereochemistry” (Eds.: Eliel, Ernest L.; Wilen, Samuel H.; Doyle, Michael P.; 2001; John Wiley & Sons) and “Stereochemisty of Organic Compounds (Eds.: Eliel, Ernest L.; Wilen, Samuel H.; Mander, Lewis N.; 1994; John Wiley & Sons), the relevant disclosure of which is incorporated by reference into the present invention. Suitable for this purpose are, for example, adduct formation with an optically active auxiliary reagent, separation of the diastereomeric adducts into the corresponding diastereomers, for example by crystallization, chromatographic methods, especially column chromatography and high pressure liquid chromatography, distillation, if appropriate under reduced pressure, extraction and other methods and subsequent cleavage of the diastereomers to afford the enantiomers. Suitable for preparative amounts or on an industrial scale are processes such as the crystallization of diastereomeric salts which can be obtained from the compounds (I) using optically active acids and, if appropriate, provided that acidic groups are present, using optically active bases.

Optically active acids which are suitable for racemate separation by crystallization of diastereomeric salts are, for example, camphorsulfonic acid, camphoric acid, bromocamphorsulfonic acid, quinic acid, tartaric acid, dibenzoyltartaric acid and other analogous acids; suitable optically active bases are, for example, quinine, cinchonine, quinidine, brucine, 1-phenylethylamine and other analogous bases.

The crystallizations are then in most cases carried out in aqueous or aqueous-organic solvents, where the diastereomer which is less soluble precipitates first, if appropriate after seeding. One enantiomer of the compound of the formula (I) is then liberated from the precipitated salt, or the other is liberated from the crystals, by acidification or using a base.

Furthermore, racemates can be separated chromatographically using chiral stationary phases. Such enantiomer separations can be carried out in the mg to 100 kg range using preparative HPLC units operated batchwise or continuously.

The “inert solvents” referred to in the above process variants are in each case solvents which are inert under the particular reaction conditions, i.e. do not react with the starting materials in particular, but need not be inert under all reaction conditions.

Libraries of compounds of the formula (I) and/or salts thereof which can be synthesized by the aforementioned reactions can also be prepared in a parallel manner, it being possible for this to take place in a manual, partly automated or completely automated manner. In this connection, it is, for example, possible to automate the reaction procedure, the work-up or the purification of the products and/or intermediates. Overall, this is understood as meaning a procedure as described, for example, by D. Tiebes in Combinatorial Chemistry—Synthesis, Analysis, Screening (editor Günther Jung), Verlag Wiley 1999, on pages 1 to 34.

For the parallel reaction procedure and work-up, it is possible to use a series of commercially available instruments, for example Calypso reaction blocks from Barnstead International, Dubuque, Iowa 52004-0797, USA or reaction stations from Radleys, Shirehill, Saffron Walden, Essex, CB 11 3AZ, England or MultiPROBE Automated Workstations from Perkin Elmer, Waltham, Mass. 02451, USA. For the parallel purification of compounds of the formula (I) and salts thereof or of intermediates produced during the preparation, there are available, inter alia, chromatography apparatuses, for example from ISCO, Inc., 4700 Superior Street, Lincoln, Nebr. 68504, USA.

The apparatuses listed lead to a modular procedure in which the individual process steps are automated, but between the process steps manual operations have to be carried out. This can be circumvented by using partly or completely integrated automation systems in which the respective automation modules are operated, for example, by robots. Automation systems of this type can be acquired, for example, from Caliper, Hopkinton, Mass. 01748, USA.

The implementation of single or several synthesis steps can be supported through the use of polymer-supported reagents/scavenger resins. The specialist literature describes a series of experimental protocols, for example in Chem Files, Vol. 4, No. 1, Polymer-Supported Scavengers and Reagents for Solution-Phase Synthesis (Sigma-Aldrich).

Besides the methods described here, the preparation of compounds of the formula (I) and salts thereof can take place completely or partially by solid-phase supported methods. For this purpose, individual intermediates or all intermediates in the synthesis or a synthesis adapted for the corresponding procedure are bonded to a synthesis resin. Solid-phase supported synthesis methods are sufficiently described in the specialist literature, e.g. Barry A. Bunin in “The Combinatorial Index”, Verlag Academic Press, 1998 and Combinatorial Chemistry—Synthesis, Analysis, Screening (editor Günther Jung), Verlag Wiley, 1999. The use of solid-phase supported synthesis methods permits a series of protocols known in the literature, which again can be carried out manually or in an automated manner. For example, the “teabag method” (Houghten, U.S. Pat. No. 4,631,211; Houghten et al., Proc. Natl. Acad. Sci., 1985, 82, 5131-5135), in which products from IRORI, 11149 North Torrey Pines Road, La Jolla, Calif. 92037, USA, are employed, may be semiautomated. The automation of solid-phase supported parallel syntheses is performed successfully, for example, by apparatuses from Argonaut Technologies, Inc., 887 Industrial Road, San Carlos, Calif. 94070, USA or MultiSynTech GmbH, Wullener Feld 4, 58454 Witten, Germany. The reactions can be carried out, for example, by means of IRORI technology in microreactors from Nexus Biosystems, 12140 Community Road, Poway, Calif. 92064, USA.

Both on solid phase and in liquid phase, the procedure of individual or several synthesis steps can be supported through the use of microwave technology. The specialist literature describes a series of experimental protocols, for example in Microwaves in Organic and Medicinal Chemistry (editor C. O. Kappe and A. Stadler), Verlag Wiley, 2005.

The preparation according to the process described here produces compounds of the formula (I) and their salts in the form of substance collections which are called libraries.

The present invention also provides libraries which comprise at least two compounds of the formula (I) and their salts.

On account of the herbicidal property of the compounds of the formula (I), the invention also further provides the use of the compounds of the formula (I) according to the invention as herbicides for controlling harmful plants.

The compounds of the formula (I) according to the invention and their salts, also referred to synonymously below together as compounds of the formula (I), have excellent herbicidal efficacy against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants. Difficult-to-control perennial weeds which produce shoots from rhizomes, root stocks or other perennial organs are also well controlled by the active compounds. Here, it is immaterial whether the substances are applied by the presowing method, the pre-emergence method or the post-emergence method.

Specific examples may be mentioned of some representatives of the monocotyledonous and dicotyledonous weed flora which can be controlled by the compounds of the formula (I) according to the invention, without the enumeration being restricted to certain species.

On the side of the monocotyledonous weed species, e.g. Agrostis, Alopecurus, Apera, Avena, Brachicaria, Bromus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Festuca, Fimbristylis, Ischaemum, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Sagittaria, Scirpus, Setaria, Sphenoclea, and also Cyperus species predominantly from the annual group and on the sides of the perennial species Agropyron, Cynodon, Imperata and Sorghum and also perennial Cyperus species are well controlled.

In the case of dicotyledonous weed species, the spectrum of action extends to species such as, for example, Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Matricaria, Abutilon and Sida on the annual side, and Convolvulus, Cirsium, Rumex and Artemisia in the case of the perennial weeds. Moreover, herbicidal effect in the case of dicotyledonous weeds such as Ambrosia, Anthemis, Carduus, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Emex, Galeopsis, Galinsoga, Lepidium, Lindernia, Papaver, Portlaca, Polygonum, Ranunculus, Rorippa, Rotala, Seneceio, Sesbania, Solanum, Sonchus, Taraxacum, Trifolium, Urtica and Xanthium is observed.

If the compounds of the formula (I) according to the invention are applied to the soil surface before germination, the weed seedlings are either prevented completely from emerging or else the weeds grow until they have reached the cotyledon stage, but then their growth stops, and, eventually, after three to four weeks have elapsed, they die completely.

If the active compounds of the formula (I) are applied post-emergence to the green parts of the plants, growth likewise stops drastically a very short time after the treatment, and the weed plants remain at the growth stage at the point of time of application, or they die completely after a certain time, so that in this manner competition by the weeds, which is harmful to the crop plants, is eliminated very early and in a sustained manner.

Although the compounds of the formula (I) according to the invention have excellent herbicidal activity in respect of monocotyledonous and dicotyledonous weeds, crop plants of economically important crops, such as, for example, wheat, barley, rye, rice, corn, sugarbeet, cotton, rapeseed and soybean, are only damaged negligibly, if at all.

This is why the present compounds are highly suitable for the selective control of unwanted plant growth in crops of agriculturally useful plants.

In addition, the substances of the formula (I) according to the invention have excellent growth regulatory properties in crop plants. They engage in the plant metabolism in a regulatory fashion and can therefore be employed for the influencing, in a targeted manner, of plant constituents and for facilitating harvesting, such as, for example, by triggering desiccation and stunted growth. Moreover, they are also suitable for generally controlling and inhibiting unwanted vegetative growth without destroying the plants in the process. Inhibiting the vegetative growth plays an important role in many monocotyledonous and dicotyledonous crops since lodging can be reduced, or prevented completely, hereby.

By virtue of their herbicidal and plant-growth-regulatory properties, the active compounds can also be employed for controlling harmful plants in crops of known genetically modified plants or genetically modified plants still to be developed. In general, the transgenic plants are distinguished by especially advantageous properties, for example by resistances to certain pesticides, mainly certain herbicides, resistances to plant diseases or causative organisms of plant diseases, such as certain insects or microorganisms such as fungi, bacteria or viruses. Other specific characteristics relate, for example, to the harvested material with regard to quantity, quality, storability, composition and specific constituents. Thus, transgenic plants are known whose starch content is increased, or whose starch quality is altered, or those where the harvested material has a different fatty acid composition. Other particular properties may be tolerance or resistance to abiotic stressors, for example heat, low temperatures, drought, salinity and ultraviolet radiation.

It is preferred to use the compounds of the formula (I) according to the invention or salts thereof in economically important transgenic crops of useful plants and ornamentals, for example of cereals such as wheat, barley, rye, oats, sorghum and millet, rice, cassaya and corn or else crops of sugar beet, cotton, soybean, oilseed rape, potato, tomato, peas and other vegetables.

It is preferred to employ the compounds of the formula (I) as herbicides in crops of useful plants which are resistant, or have been made resistant by recombinant means, to the phytotoxic effects of the herbicides.

Conventional methods of generating novel plants which have modified properties in comparison to plants occurring to date consist, for example, in traditional breeding methods and the generation of mutants. Alternatively, novel plants with altered properties can be generated with the aid of recombinant methods (see, for example, EP 0221044, EP 0131624). For example, the following have been described in several cases:

    • recombinant modifications of crop plants for the purposes of modifying the starch synthesized in the plants (for example WO 92/011376, WO 92/014827, WO 91/019806),
    • transgenic crop plants which are resistant to certain herbicides of the glufosinate type (cf., for example, EP 0242236, EP 0242246) or the glyphosate type (WO 92/00377) or the sulfonylurea type (EP 0257993, U.S. Pat. No. 5,013,659),
    • transgenic crop plants, for example cotton, which is capable of producing Bacillus thuringiensis toxins (Bt toxins), which make the plants resistant to certain pests (EP 0142924, EP 0193259),
    • transgenic crop plants with a modified fatty acid composition (WO 91/013972).
    • genetically modified crop plants with novel constituents or secondary metabolites, for example novel phytoalexins, which bring about an increased disease resistance (EP 0309862, EP 0464461),
    • genetically modified plants with reduced photorespiration which feature higher yields and higher stress tolerance (EP 0305398),
    • transgenic crop plants which produce pharmaceutically or diagnostically important proteins (“molecular pharming”),
    • transgenic crop plants which are distinguished by higher yields or better quality,
    • transgenic crop plants which are distinguished by a combination, for example of the abovementioned novel properties (“gene stacking”).

A large number of molecular-biological techniques by means of which novel transgenic plants with modified properties can be generated are known in principle; see, for example, I. Potrykus and G. Spangenberg (eds.) Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg. or Christou, “Trends in Plant Science” 1 (1996) 423-431).

To carry out such recombinant manipulations, nucleic acid molecules which allow mutagenesis or sequence changes by recombination of DNA sequences can be introduced into plasmids. For example, base substitutions can be carried out, part-sequences can be removed, or natural or synthetic sequences may be added with the aid of standard methods. To link the DNA fragments with one another, it is possible to add adapters or linkers to the fragments; see, for example, Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed., Cold Spring Harbor Laboratory Press, Cold Spring Harbor, N.Y.; or Winnacker “Gene and Klone”, VCH Weinheim 2nd ed., 1996.

For example, the generation of plant cells with a reduced activity of a gene product can be achieved by expressing at least one corresponding antisense RNA, a sense RNA for achieving a cosuppression effect or by expressing at least one suitably constructed ribozyme which specifically cleaves transcripts of the abovementioned gene product.

To this end, it is possible to use DNA molecules which encompass the entire coding sequence of a gene product inclusive of any flanking sequences which may be present, and also DNA molecules which only encompass portions of the coding sequence, it being necessary for these portions to be long enough to have an antisense effect in the cells. The use of DNA sequences which have a high degree of homology to the coding sequences of a gene product, but are not completely identical to them, is also possible.

When expressing nucleic acid molecules in plants, the protein synthesized can be localized in any desired compartment of the plant cell. However, to achieve localization in a particular compartment, it is possible, for example, to link the coding region with DNA sequences which ensure localization in a particular compartment. Such sequences are known to those skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106). The nucleic acid molecules can also be expressed in the organelles of the plant cells.

The transgenic plant cells can be regenerated by known techniques to give rise to entire plants. In principle, the transgenic plants can be plants of any desired plant species, i.e. not only monocotyledonous, but also dicotyledonous, plants.

Thus, transgenic plants can be obtained whose properties are altered by overexpression, suppression or inhibition of homologous (=natural) genes or gene sequences or the expression of heterologous (=foreign) genes or gene sequences.

It is preferred to employ the compounds of the formula (I) according to the invention in transgenic crops which are resistant to growth regulators such as, for example, dicamba, or against herbicides which inhibit essential plant enzymes, for example acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or hydroxyphenylpyruvate dioxygenases (HP PD), or against herbicides from the group of the sulfonylureas, glyphosate, glufosinate or benzoylisoxazoles and analogous active substances.

When the active compounds of the formula (I) according to the invention are used in transgenic crops, effects are frequently observed—in addition to the effects on harmful plants which can be observed in other crops—which are specific for the application in the transgenic crop in question, for example a modified or specifically widened spectrum of weeds which can be controlled, modified application rates which may be employed for application, preferably good combinability with the herbicides to which the transgenic crop is resistant, and an effect on growth and yield of the transgenic crop plants.

The invention therefore also relates to the use of the compounds of the formula (I) according to the invention as herbicides for controlling harmful plants in transgenic crop plants.

The compounds of the formula (I) can be formulated in various ways according to which biological and/or physicochemical parameters are required. Possible formulations include, for example: wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW) such as oil-in-water and water-in-oil emulsions, sprayable solutions, suspension concentrates (SC), oil- or water-based dispersions, oil-miscible solutions, capsule suspensions (CS), dusting products (DP), seed-dressing products, granules for scattering and soil application, granules (GR) in the form of microgranules, spray granules, coated granules and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes.

These individual types of formulation are known in principle and are described, for example, in: Winnacker-Küchler, “Chemische Technologie” [Chemical technology], Volume 7, C. Hanser Verlag Munich, 4th Ed. 1986, Wade van Valkenburg, “Pesticide Formulations”, Marcel Dekker, N.Y., 1973; K. Martens, “Spray Drying” Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London.

The necessary formulation assistants, such as inert materials, surfactants, solvents and further additives, are likewise known and are described, for example, in: Watkins, “Handbook of Insecticide Dust Diluents and Carriers”, 2nd Ed., Darland Books, Caldwell N.J., H.v. Olphen, “Introduction to Clay Colloid Chemistry”; 2nd Ed., J. Wiley & Sons, N.Y.; C. Marsden, “Solvents Guide”; 2nd Ed., Interscience, N.Y. 1963; McCutcheon's “Detergents and Emulsifiers Annual”, MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, “Encyclopedia of Surface Active Agents”, Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt, “Grenzf{umlaut over (l)}achenaktive Äthylenoxidaddukte” [Interface-active ethylene oxide adducts], Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Küchler, “Chemische Technologie”, Volume 7, C. Hanser Verlag Munich, 4th Ed. 1986.

Based on these formulations, it is also possible to produce combinations with other pesticidally active compounds, such as, for example, insecticides, acaricides, herbicides, fungicides, and also with safeners, fertilizers and/or growth regulators, for example in the form of a finished formulation or as a tank mix.

Wettable powders are preparations which can be dispersed uniformly in water and, as well as the active compound, apart from a diluent or inert substance, also comprise surfactants of the ionic and/or nonionic type (wetting agents, dispersants), for example polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, sodium lignosulfonate, sodium 2,2′-dinaphthylmethane-6,6′-disulfonate, sodium dibutylnaphthalenesulfonate or else sodium oleylmethyltauride. To prepare the wettable powders, the herbicidally active compounds are ground finely, for example in customary apparatus such as hammer mills, blower mills and air-jet mills and simultaneously or subsequently mixed with the formulation assistants.

Emulsifiable concentrates are prepared by dissolving the active compound in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or else relatively high-boiling aromatics or hydrocarbons or mixtures of the organic solvents with addition of one or more surfactants of the ionic and/or nonionic type (emulsifiers). The emulsifiers used may, for example, be: alkylarylsulfonic calcium salts, such as calcium dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters, such as, for example, sorbitan fatty acid esters, or polyoxyethylene sorbitan esters, such as, for example, polyoxyethylene sorbitan fatty acid esters.

Dusts are obtained by grinding the active compound with finely distributed solid substances, for example talc, natural clays, such as kaolin, bentonite and pyrophillite, or diatomaceous earth.

Suspension concentrates may be water- or oil-based. They may be prepared, for example, by wet grinding by means of commercial bead mills and optional addition of surfactants as have, for example, already been listed above for the other formulation types.

Emulsions, e.g. oil-in-water emulsions (EW), can be prepared, for example, by means of stirrers, colloid mills and/or static mixers using aqueous organic solvents and if appropriate surfactants, as have for example already been listed above in connection with the other types of formulation.

Granules can be prepared either by spraying the active compound onto granular inert material capable of adsorption or by applying active compound concentrates to the surface of carrier substances, such as sand, kaolinites or granular inert material, by means of adhesives, for example polyvinyl alcohol, sodium polyacrylate or mineral oils. Suitable active compounds can also be granulated in the manner customary for the preparation of fertilizer granules—if desired as a mixture with fertilizers.

Water-dispersible granules are prepared generally by the customary processes such as spray-drying, fluidized bed granulation, pan granulation, mixing with high-speed mixers and extrusion without solid inert material. For the preparation of pan, fluidized bed, extruder and spray granules, see, for example, processes in “Spray-Drying Handbook” 3rd ed. 1979, G. Goodwin Ltd., London; J. E. Browning, “Agglomeration”, Chemical and Engineering 1967, pages 147 ff; “Perry's Chemical Engineer's Handbook”, 5th Ed., McGraw-Hill, New York 1973, pp. 8-57.

For further details regarding the formulation of crop protection compositions, see, for example, G. C. Klingman, “Weed Control as a Science”, John Wiley and Sons, Inc., New York, 1961, pages 81-96 and J. D. Freyer, S. A. Evans, “Weed Control Handbook”, 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103.

The agrochemical formulations comprise generally from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of active compound of the formula (I).

In wettable powders, the active compound concentration is, for example, from about 10 to 90% by weight, the remainder to 100% by weight consisting of customary formulation components. In the case of emulsifiable concentrates, the active compound concentration can be from about 1 to 90, preferably from 5 to 80, % by weight. Dust-type formulations contain from 1 to 30% by weight of active compound, preferably usually from 5 to 20% by weight of active compound; sprayable solutions contain from about 0.05 to 80% by weight, preferably from 2 to 50% by weight of active compound. In the case of water-dispersible granules, the active compound content depends partially on whether the active compound is present in liquid or solid form and on which granulation auxiliaries, fillers, etc., are used. In the water-dispersible granules, the content of active compound is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.

In addition, the active compound formulations mentioned optionally comprise the respective customary adhesives, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents and solvents, fillers, carriers and dyes, defoamers, evaporation inhibitors and agents which influence the pH and the viscosity.

The compounds of the formula (I) or salts thereof can be employed as such or in the form of their preparations (formulations) combined with other pesticidally active compounds, such as, for example, insecticides, acaricides, nematicides, herbicides, fungicides, safeners, fertilizers and/or growth regulators, for example as finished formulation or as tank mix. Combination partners which can be used for the active compounds of the formula (I) in mixture formulations or in the tank mix are, for example, known active compounds whose action is based on the inhibition of, for example, acetolactate synthase, acetyl-coenzyme-A carboxylase, PS I, PS II, HPPDO, phytoene desaturase, protoporphyrinogen oxidase, glutamine synthetase, 5-enolpyruvylshikimate 3-phosphate synthetase or cellulose biosynthesis. Such compounds and also other compounds that can be used, some of which having an unknown or other mechanism of action, are described, for example, in Weed Research 26, 441-445 (1986), or “The Pesticide Manual”, 11th edition 1997 (hereinbelow also referred to abbreviated as “PM”) and 12th edition 2000, The British Crop Protection Council and the Royal Soc. of Chemistry (publisher), and the literature cited therein. Herbicides known from the literature which can be combined with the compounds of the formula (I) are, for example, the following active compounds (note: the compounds are referred to either by the “common name” in accordance with the International Organization for Standardization (ISO) or by the chemical name, if appropriate together with a customary code number):

  • acetochlor; acifluorfen(-sodium); aclonifen; AKH 7088, i.e. [[[1-[5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrophenyl]-2-methoxyethylidene]amino]oxy]acetic acid and methyl [[[1-[5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrophenyl]-2-methoxyethylidene]amino]oxy]acetate; acrolein; alachlor; alloxydim(-sodium); ametryn; amicarbazone, amidochlor, amidosulfuron; aminopyralid, amitrol; AMS, i.e. ammonium sulfamate; anilofos; asulam; atraton; atrazine; azafenidin, azimsulfuron (DPX-A8947); aziprotryn; barban; BAS 516 H, i.e. 5-fluoro-2-phenyl-4H-3,1-benzoxazin-4-one; BCPC; beflubutamid, benazolin(-ethyl); benfluralin; benfuresate; bensulfuron(-methyl); bensulide; bentazone; benzfendizone; benzobicyclon, benzofenap; benzofluor; benzoylprop(-ethyl); benzthiazuron; bifenox; bialaphos; bifenox; bispyribac(-sodium), borax; bromacil; bromobutide; bromofenoxim; bromoxynil; bromuron; buminafos; busoxinone; butachlor; butafenacil, butamifos; butenachlor; buthidazole; butralin; butroxydim, butylate; cacodylic acid; calcium chlorate; cafenstrole (CH-900); carbetamide; carfentrazone(-ethyl); caloxydim, CDAA, i.e. 2-chloro-N,N-di-2-propenylacetamide; CDEC, i.e. 2-chlorallyl diethyldithiocarbamate; chlorflurenol (-methyl); chlomethoxyfen; clethodim; clomeprop; chloramben; chlorazifop-butyl, chlormesulon; chlorbromuron; chlorbufam; chlorfenac; chlorflurecol-methyl; chloridazon; chlorimuron(-ethyl); chloroacetic acid; chlornitrofen; chlorotoluron; chloroxuron; chlorpropham; chlorsulfuron; chlorthal(-dimethyl); chlorthiamid; chlortoluron, cinidon(-methyl and -ethyl), cinmethylin; cinosulfuron; cisanilide; clefoxydim, clethodim; clodinafop and its ester derivatives (for example clodinafop-propargyl); clomazone; clomeprop; cloproxydim; clopyralid; clopyrasulfuron(-methyl); cloransulam(-methyl), cresol; cumyluron (JC 940); cyanamide; cyanazine; cycloate; cyclosulfamuron (AC 104); cycloxydim; cycluron; cyhalofop and its ester derivatives (for example the butyl ester, DEH-112); cyperquat; cyprazine; cyprazole; daimuron; 2,4-D, 2,4-DB, 3,4-DA, 3,4-DB, 2,4-DEB, dalapon; dazomed; desmedipham; desmetryn; di-allate; dicamba; dichlobenil; ortho-dichlorobenzene; para-dichlorobenzene; dichlorprop; dichlorprop-P; diclofop and its esters, such as diclofop-methyl; diclosulam, diethatyl(-ethyl); difenoxuron; difenzoquat; difenzoquat-methylsulfate; diflufenican; diflufenzopyr, dimefuron; dimepiperate, dimethachlor; dimethametryn; dimethenamid (SAN-582H); dimethenamid-P; dimethazone, dimexyflam, dimethipin; dimethylarsinic acid; dimetrasulfuron, dinitramine; dinoseb; dinoterb; diphenamid; dipropetryn; diquat; diquat-dibromide; dithiopyr; diuron; DNOC; 3,4-DP; DSMA; EBEP; eglinazine-ethyl; EL77, i.e. 5-cyano-1-(1,1-dimethylethyl)-N-methyl-1H-pyrazole-4-carboxamide; endothal; epoprodan, EPTC; esprocarb; ethalfluralin; ethametsulfuron(-methyl); ethidimuron; ethiozin; ethofumesate; ethoxyfen and its esters (for example the ethyl ester, HN-252); ethoxysulfuron, etobenzanid (HW 52); F5231, i.e. N-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-4,5-dihydro-5-oxo-1H-tetrazol-1-yl]phenyl]ethanesulfonamide; fenoprop; fenoxan, fenoxapropand fenoxaprop-P and also their esters, for example fenoxaprop-P-ethyl and fenoxaprop-ethyl; fenoxydim; fentrazamide, fenuron; ferrous sulfate; flamprop(-methyl or -isopropyl or -isopropyl-L); flazasulfuron; floazulate, florasulam, fluazifop and fluazifop-P and their esters, for example fluazifop-butyl and fluazifop-P-butyl; fluazolate; flucarbazone(-sodium), flucetosulfuron; fluchloralin; flufenacet; flufenpyr(-ethyl); flumetsulam; flumeturon; flumiclorac(-pentyl), flumioxazin (S-482); flumipropyn; fluometuron, fluorochloridone, fluorodifen; fluoroglycofen(-ethyl); flupoxam (KNW-739); flupropacil (UBIC-4243); flupropanate, flupyrsulfuron(-methyl or -sodium), flurenol(-butyl), fluridone; fluorochloridone; fluoroxypyr(-meptyl); flurprimidol; flurtamone; fluthiacet(-methyl) (KIH-9201); fluthiamide; fomesafen; foramsulfuron; fosamine; furyloxyfen; glufosinate(-ammonium); glyphosate(-isopropylammonium); halosafen; halosulfuron(-methyl) and its esters (for example the methyl ester, NC-319); haloxyfop and its esters; haloxyfop-P (=R-haloxyfop) and its esters; HC-252; hexazinone; imazamethabenz(-methyl); imazapyr; imazaquin and salts, such as the ammonium salt; imazamethapyr, imazamox, imazapic, imazethamethapyr; imazethapyr; imazosulfuron; indanofan, iodomethane; iodosulfuron(methylsodium); ioxynil; isocarbamid; isopropalin; isoproturon; isouron; isoxaben; isoxachlortole, isoxaflutole, isoxapyrifop; karbutilate; lactofen; lenacil; linuron; MAA; MAMA; MCPA; MCPA-2-ethylhexyl; MCPA-thioethyl; MCPB; mecoprop; mecoprop-P; mefenacet; mefluidid; mesosulfuron(-methyl); mesotrione, metamifop; metamitron; metazachlor; methabenzthiazuron; metham; methazole; methoxyphenone; methylarsonic acid; methyldymron; methyl isothiocyanate; metabenzuron, metamifop; methobenzuron; metobromuron; (alpha-)metolachlor; S-metolachlor; metosulam (XRD 511); metoxuron; metribuzin; metsulfuron-methyl; MK-616; MH; molinate; monalide; monocarbamide dihydrogensulfate; monolinuron; monuron; MSMA; MT 128, i.e. 6-chloro-N-(3-chloro-2-propenyl)-5-methyl-N-phenyl-3-pyridazinamine; MT 5950, i.e. N-[3-chloro-4-(1-methylethyl)phenyl]-2-methylpentanamide; naproanilide; napropamide; naptalam; NC 310, i.e. 4-(2,4-dichlorobenzoyl)-1-methyl-5-benzyloxypyrazole; neburon; nicosulfuron; nipyraclophen; nitralin; nitrofen; nitrofluorfen; nonanoic acid; norflurazon; oleic acid (fatty acid); orbencarb; orthosulfamuron; oryzalin; oxadiargyl (RP-020630); oxadiazon; oxasulfuron, oxaziclomefone, oxyfluorfen; paraquat; paraquat-dichloride; pebulate; pelargonic acid, pendimethalin; penoxsulam; pentachlorophenol; pentanochlor; pentoxazone, perfluidone; phenisopham; phenmedipham(ethyl); pethoxamid; picloram; picolinafen, pinoxaden, piperophos; piributicarb; pirifenop-butyl; pretilachlor; primisulfuron(-methyl); potassium arsenite; potassium azide; procarbazone-(sodium), procyazine; prodiamine; profluazol; profluralin; profoxydim; proglinazine(-ethyl); prometon; prometryn; propachlor; propanil; propaquizafop and its esters; propazine; propham; propisochlor; propoxycarbazone(-sodium) (BAY MKH 6561); propyzamide; prosulfalin; prosulfocarb; prosulfuron (CGA-152005); prynachlor; pyraclonil; pyraflufen(-ethyl), pyrasulfotole; pyrazolinate; pyrazon; pyrazosulfuron(-ethyl); pyrazoxyfen; pyribambenzisopropyl; pyribenzoxim, pyributicarb, pyridafol, pyridate; pyriftalid; pyrimidobac(-methyl), pyrimisulfan, pyrithiobac(-sodium) (KIN-2031); pyroxasulfone; pyroxofop and its esters (for example the propargyl ester); pyroxsulam (triflosulam); quinclorac; quinmerac; quinoclamine, quinofop and its ester derivatives, quizalofop and quizalofop-P and their ester derivatives, for example quizalofop-ethyl; quizalofop-P-tefuryl and -ethyl; renriduron; rimsulfuron (DPX-E 9636); S 275, i.e. 2-[4-chloro-2-fluoro-5-(2-propynyloxy)phenyl]-4,5,6,7-tetrahydro-2H-indazole; secbumeton; sethoxydim; siduron; simazine; simetryn; SN 106279, i.e. 2-[[7-[2-chloro-4-(trifluoromethyl)phenoxy]-2-naphthalenyl]oxy]propanoic acid and methyl 2-[[7-[2-chloro-4-(trifluoromethyl)phenoxy]-2-naphthalenyl]oxy]propanoate; SMA; sodium arsenite; sodium azide; sodium chlorate; sulcotrione, sulfentrazon (FMC-97285, F-6285); sulfazuron; sulfometuron(-methyl); sulfosate (ICI-A0224); sulfosulfuron, 2,3,6-TBA; TCA(sodium); tebutam (GCP-5544); tebuthiuron; tefuryltrione, tembotrione, tepraloxydim, terbacil; terbucarb; terbuchlor; terbumeton; terbuthylazine; terbutryn; TFH 450, i.e. N,N-diethyl-3-[(2-ethyl-6-methylphenyl)sulfonyl]-1H-1,2,4-triazole-1-carboxamide; thenylchlor (NSK-850); thiafluamide, thiazafluoron; thiazopyr (Mon-13200); thidiazimin (SN-24085); thiencarbazone-methyl, thifensulfuron(-methyl); thiobencarb; tiocarbazil; tralkoxydim; tri-allate; triasulfuron; triaziflam, triazofenamide; tribenuron(-methyl); tricamba; triclopyr; tridiphane; trietazine; trifloxysulfuron(sodium); trifluralin; triflusulfuron and esters (for example the methyl ester, DPX-66037); trihydroxytriazine; trimeturon; tritosulfuron; tropamezone; tsitodef; vernolate; [3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetic acid ethyl ester; WL 110547, i.e. 5-phenoxy-1-[3-(trifluoromethyl)phenyl]-1H-tetrazole; UBH-509; D-489; LS 82-556, i.e. [(S)-3-N-(methylbenzyl)carbamoyl-5-propionyl-2,6-lutidine]; KPP-300; NC-324; NC-330; KH-218; DPX-N8189; SC-0774; DOWCO-535; DK-8910; V-53482; PP-600; MBH-001; ET-751, i.e. ethyl [2-chloro-5-(4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl)-4-fluorophenoxy]acetate; KIH-6127, i.e. pyriminobac-methyl; KIH-2023, i.e. bispyribac-sodium; and SYP-249, i.e ethyl 2-{2-nitro-5-[(2-chloro-4-trifluoromethyl)phenoxy]benzoxy}-3-methyl-3-butenoate; SYN-523.

Of particular interest is the selective control of harmful plants in crops of useful plants and ornamental plants. Although the compounds of the formula (I) according to the invention have already demonstrated very good to adequate selectivity in a large number of crops, in principle, in some crops and in particular also in the case of mixtures with other, less selective herbicides, phytotoxicities on the crop plants may occur. In this connection, combinations of compounds of the formula (I) according to the invention are of particular interest which comprise the compounds of the formula (I) or their combinations with other herbicides or pesticides and safeners. The safeners, which are used in an antidotically effective amount, reduce the phytotoxic side effects of the herbicides/pesticides employed, for example in economically important crops, such as cereals (wheat, barley, rye, corn, rice, sorghum and millet), sugar beet, sugar cane, oilseed rape, cotton and soybean, preferably cereals. The following groups of compounds are suitable, for example, as safeners for the compounds (I) alone or else in their combinations with further pesticides:

  • a) compounds of the formulae (S-II) to (S-IV)
    where the symbols and indices have the following meanings:

  • n′ is a natural number from 0 to 5, preferably from 0 to 3;
  • T is a (C1- or C2)-alkanediyl chain which is unsubstituted or substituted by one or two (C1-C4)-alkyl radicals or by [(C1-C3)-alkoxy]carbonyl;
  • W is an unsubstituted or substituted divalent heterocyclic radical from the group consisting of partially unsaturated or aromatic five-membered heterocycles having 1 to 3 hetero ring atoms of the type N or O, where at least one nitrogen atom and at most one oxygen atom is present in the ring, preferably a radical from the group consisting of (W1) to (W4),

  • m′ is 0 or 1;
  • R17, R19 are identical or different and are halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, nitro or (C1-C4)-haloalkyl;
  • R18, R20 are identical or different and are OR24, SR24 or NR24R25 or a saturated or unsaturated 3- to 7-membered heterocycle having at least one nitrogen atom and up to 3 heteroatoms, preferably from the group consisting of O and S, which is attached via the nitrogen atom to the carbonyl group in (S-II) or (S-III) and is unsubstituted or substituted by radicals from the group consisting of (C1-C4)-alkyl, (C1-C4)-alkoxy or optionally substituted phenyl, preferably a radical of the formula OR24, NHR25 or N(CH3)2, in particular of the formula OR24;
  • R24 is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical having preferably a total of 1 to 18 carbon atoms;
  • R25 is hydrogen, (C1-C6)-alkyl, (C1-C6)-alkoxy or substituted or unsubstituted phenyl;
  • RX′ is H, (C1-C8)-alkyl, (C1-C8)-haloalkyl, (C1-C4)-alkoxy-(C1-C8)-alkyl, cyano or COOR26 where R26 is hydrogen, (C1-C8)-alkyl, (C1-C8)-haloalkyl, (C1-C4)-alkoxy-(C1-C4)-alkyl, (C1-C6)-hydroxyalkyl, (C3-C12)-cycloalkyl or tri-(C1-C4)-alkylsilyl;
  • R27, R28, R29 are identical or different and are hydrogen, (C1-C8)-alkyl, (C1-C8)-haloalkyl, (C3-C12)-cycloalkyl or substituted or unsubstituted phenyl;
  • R21 is (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C2-C4)-alkenyl, (C2-C4)-haloalkenyl, (C3-C7)-cycloalkyl, preferably dichloromethyl;
  • R22, R23 are identical or different and are hydrogen, (C1-C4)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, (C1-C4)-haloalkyl, (C2-C4)-haloalkenyl, (C1-C4)-alkylcarbamoyl-(C1-C4)-alkyl, (C2-C4)-alkenylcarbamoyl-(C1-C4)-alkyl, (C1-C4)-alkoxy-(C1-C4)-alkyl, dioxolanyl-(C1-C4)-alkyl, thiazolyl, furyl, furylalkyl, thienyl, piperidyl, substituted or unsubstituted phenyl, or R22 and R23 together form a substituted or unsubstituted heterocyclic ring, preferably an oxazolidine, thiazolidine, piperidine, morpholine, hexahydropyrimidine or benzoxazine ring;
  • b) one or more compounds from the group consisting of:
    • 1,8-naphthalic anhydride,
    • methyl diphenylmethoxyacetate,
    • 1-(2-chlorobenzyl)-3-(1-methyl-1-phenylethyl)urea (cumyluron),
    • O,O-diethyl S-2-ethylthioethyl phosphorodithioate (disulfoton),
    • 4-chlorophenyl methylcarbamate (mephenate),
    • O,O-diethyl O-phenyl phosphorothioate (dietholate),
    • 4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid (CL-304415, CAS-Regno: 31541-57-8),
    • cyanomethoxyimino(phenyl)acetonitrile (cyometrinil)
    • 1,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile (oxabetrinil),
    • 4′-chloro-2,2,2-trifluoroacetophenone O-1,3-dioxolan-2-ylmethyloxime (fluxofenim),
    • 4,6-dichloro-2-phenylpyrimidine (fenclorim),
    • benzyl 2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate (flurazole),
    • 2-dichloromethyl-2-methyl-1,3-dioxolane (MG-191),
    • N-(4-methylphenyl)-N′-(1-methyl-1-phenylethyl)urea (dymron),
    • (2,4-dichlorophenoxy)acetic acid (2,4-D),
    • (4-chlorophenoxy)acetic acid,
    • (R,S)-2-(4-chloro-o-tolyloxy)propionic acid (mecoprop),
    • 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB),
    • (4-chloro-o-tolyloxy)acetic acid (MCPA),
    • 4-(4-chloro-o-tolyloxy)butyric acid,
    • 4-(4-chlorophenoxy)butyric acid,
    • 3,6-dichloro-2-methoxybenzoic acid (dicamba),
    • 1-(ethoxycarbonyl)ethyl 3,6-dichloro-2-methoxybenzoate (lactidichlor)
    • and their salts and esters, preferably (C1-C8);
  • c) N-acylsulfonamides of the formula (S-V) and their salts,


in which

  • R30 is hydrogen, a hydrocarbon radical, a hydrocarbonoxy radical, a hydrocarbonthio radical or a heterocyclyl radical which is preferably attached via a carbon atom, where each of the 4 last-mentioned radicals is unsubstituted or substituted by one or more identical or different radicals from the group consisting of halogen, cyano, nitro, amino, hydroxyl, carboxyl, formyl, carbonamide, sulfonamide and radicals of the formula —Za′—Ra′,
    • where each hydrocarbon moiety has preferably 1 to 20 carbon atoms and a carbon-containing radical R30 including substituents has preferably 1 to 30 carbon atoms;
  • R31 is hydrogen or (C1-C4)-alkyl, preferably hydrogen, or
  • R30 and R31 together with the group of the formula —CO—N— are the radicals of a 3- to 8-membered saturated or unsaturated ring;
  • R32 are identical or different radicals from the group consisting of halogen, cyano, nitro, amino, hydroxyl, carboxyl, formyl, CONH2, SO2NH2 or a radical of the formula —Zb′—Rb′;
  • R33 is hydrogen or (C1-C4)-alkyl, preferably H;
  • R34 are identical or different radicals from the group consisting of halogen, cyano, nitro, amino, hydroxyl, carboxyl, CHO, CONH2, SO2NH2 and a radical of the formula —Zc′—Rc′;
  • Ra′ is a hydrocarbon radical or a heterocyclyl radical, where each of the two last-mentioned radicals is unsubstituted or substituted by one or more identical or different radicals from the group consisting of halogen, cyano, nitro, amino, hydroxyl, mono- and di-[(C1-C4)-alkyl]amino, or an alkyl radical in which a plurality, preferably 2 or 3, non-adjacent CH2 groups are in each case replaced by an oxygen atom;
  • Rb′, Rc′ are identical or different and are a hydrocarbon radical or a heterocyclyl radical, where each of the two last-mentioned radicals is unsubstituted or substituted by one or more identical or different radicals from the group consisting of halogen, cyano, nitro, amino, hydroxyl, phosphoryl, halo-(C1-C4)-alkoxy, mono- and di-[(C1-C4)-alkyl]amino, or an alkyl radical in which a plurality, preferably 2 or 3, non-adjacent CH2 groups are in each case replaced by an oxygen atom;
  • Za′ is a divalent group of the formula —O—, —S—, —CO—, —CS—, —CO—O—, —CO—S—, —O—CO—, —S—CO—, —SO—, —SO2—, —NR*—, —CO—NR*—, —NR*—CO—, —SO2—NR*— or —NR*—SO2—, where the bond indicated on the right-hand side of the divalent group in question is the bond to the radical Ra' and where the R* in the 5 last-mentioned radicals independently of one another are each H, (C1-C4)-alkyl or halo-(C1-C4)-alkyl;
  • Zb′, Zc′ independently of one another are a direct bond or a divalent group of the formula —O—, —S—, —CO—, —CS—, —CO—O—, —CO—S—, —O—CO—, —S—CO—, —SO—, —SO2—, —NR*—, —SO2—NR*—, —NR*—SO2—, —CO—NR*— or —NR*—CO—, where the bond indicated on the right-hand side of the divalent group in question is the bond to the radical Rb′ or Rc′ and where the R* in the 5 last-mentioned radicals independently of one another are each H, (C1-C4)-alkyl or halo-(C1-C4)-alkyl;
  • n is an integer from 0 to 4, preferably 0, 1 or 2, particularly preferably 0 or 1, and
  • m is an integer from 0 to 5, preferably 0, 1, 2 or 3, in particular 0, 1 or 2;
  • d) acylsulfamoylbenzamides of the formula (S-VI), if appropriate also in salt form,


in which

  • X3 is CH or N,
  • R35 is hydrogen, heterocyclyl or a hydrocarbon radical, where the two last-mentioned radicals are optionally substituted by one or more identical or different radicals from the group consisting of halogen, cyano, nitro, amino, hydroxyl, carboxyl, CHO, CONH2, SO2NH2 and Za′—Ra′;
  • R36 is hydrogen, hydroxyl, (C1-C6)-alkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, (C1-C6)-alkoxy, (C2-C6)-alkenyloxy, where the five last-mentioned radicals are optionally substituted by one or more identical or different radicals from the group consisting of halogen, hydroxyl, (C1-C4)-alkyl, (C1-C4)-alkoxy and (C1-C4)-alkylthio, or
  • R35 and R36 together with the nitrogen atom that carries them are a 3- to 8-membered saturated or unsaturated ring;
  • R37 is halogen, cyano, nitro, amino, hydroxyl, carboxyl, CHO, CONH2, SO2NH2 or Zb′—Rb′;
  • R38 is hydrogen, (C1-C4)-alkyl, (C2-C4)-alkenyl or (C2-C4)-alkynyl;
  • R39 is halogen, cyano, nitro, amino, hydroxyl, carboxyl, phosphoryl, CHO, CONH2, SO2NH2 or Zc′—Rc′;
  • Ra′ is a (C2-C20)-alkyl radical whose carbon chain is interrupted once or more than once by oxygen atoms, is heterocyclyl or a hydrocarbon radical, where the two last-mentioned radicals are optionally substituted by one or more identical or different radicals from the group consisting of halogen, cyano, nitro, amino, hydroxyl, mono- and di-[(C1-C4)-alkyl]amino;
  • Rb′, Rc′ are identical or different and are a (C2-C20)-alkyl radical whose carbon chain is interrupted once or more than once by oxygen atoms, are heterocyclyl or a hydrocarbon radical, where the two last-mentioned radicals are optionally substituted by one or more identical or different radicals from the group consisting of halogen, cyano, nitro, amino, hydroxyl, phosphoryl, (C1-C4)-haloalkoxy, mono- and di-[(C1-C4)-alkyl]amino;
  • Za′ is a divalent unit from the group consisting of O, S, CO, CS, C(O)O, C(O)S, SO, SO2, NRd′, C(O)NRd′ and SO2NRd′;
  • Zb′, Zc′ are identical or different and are a direct bond or a divalent unit from the group consisting of O, S, CO, CS, C(O)O, C(O)S, SO, SO2, NRd′, SO2NRd′ and C(O)NRd′;
  • Rd′ is hydrogen, (C1-C4)-alkyl or (C1-C4)-haloalkyl;
  • N is an integer from 0 to 4, and
  • m, if X is CH, is an integer from 0 to 5, and, if X is N, is an integer from 0 to 4;
  • e) compounds of the type of the acylsulfamoylbenzamides, for example of the formula (S-VII) below, which are known, for example, from WO 99/16744,


for example those in which

    • R21=cyclopropyl and R22=H(S-3-1=4-cyclopropylaminocarbonyl-N-(2-methoxybenzoyl)benzenesulfonamide),
    • R21=cyclopropyl and R22=5-Cl (S-3-2),
    • R21=ethyl and R22=H(S-3-3),
    • R21=isopropyl and R22=5-Cl (S-3-4) and
    • R21=isopropyl and R22=H(S-3-5);
  • f) compounds of the type of the N-acylsulfamoylphenylureas of the formula (S-VIII), which are known, for example, from EP-A-365484


in which

  • A is a radical from the group consisting of

  • Rα′ and Rβ′ independently of one another are hydrogen, (C1-C8)-alkyl, (C3-C8)-cycloalkyl, (C3-C6)-alkenyl, (C3-C6)-alkynyl,


or (C1-C4)-alkoxy substituted by (C1-C4)-alkoxy or

  • Rα′ and Rβ′ together are a (C4-C6)-alkylene bridge or a (C4-C6)-alkylene bridge which is interrupted by oxygen, sulfur, SO, SO2, NH or —N((C1-C4)-alkyl)-,
  • Rγ′ is hydrogen or (C1-C4)-alkyl,
  • Ra′ and Rb′ independently of one another are hydrogen, halogen, cyano, nitro, trifluoromethyl, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-alkylthio, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, —COORj, —CONRk′Rm′, —CORn′, —SO2NRk′Rm′ or —OSO2—(C1-C4)-alkyl, or Ra′ and Rb′ together are a (C3-C4)-alkylene bridge which may be substituted by halogen or (C1-C4)-alkyl, or a (C3-C4)-alkenylene bridge which may be substituted by halogen or (C1-C4)-alkyl, or a C4-alkadienylene bridge which may be substituted by halogen or (C1-C4)-alkyl, and
  • Rg′ and Rh′ independently of one another are hydrogen, halogen, (C1-C4)-alkyl, trifluoromethyl, methoxy, methylthio or —COORj′, where
  • Rc′ is hydrogen, halogen, (C1-C4)-alkyl or methoxy,
  • Rd′ is hydrogen, halogen, nitro, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-alkylthio, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, —COORj′ or —CONRk′Rm′,
  • Re′ is hydrogen, halogen, (C1-C4)-alkyl, —COORj, trifluoromethyl or methoxy, or Rd′ and Re′ together are a (C3-C4)-alkylene bridge,
  • Rf′ is hydrogen, halogen or (C1-C4)-alkyl,
  • RX′ and RY′ independently of one another are hydrogen, halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-alkylthio, —COORj′, trifluoromethyl, nitro or cyano,
  • Rj′, Rk′ and Rm′ independently of one another are hydrogen or (C1-C4)-alkyl,
  • Rk′ and Rm′ together are a C4-C6-alkylene bridge or a (C4-C6)-alkylene bridge which is interrupted by oxygen, NH or —N((C1-C4)-alkyl)-, and
  • Rn′ is (C1-C4)-alkyl, phenyl or phenyl which is substituted by halogen, (C1-C4)-alkyl, methoxy, nitro or trifluoromethyl,
    preferably
    • 1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3-methylurea,
    • 1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylurea,
    • 1-[4-(N-4,5-dimethylbenzoylsulfamoyl)phenyl]-3-methylurea,
    • 1-[4-(N-naphthoylsulfamoyl)phenyl]-3,3-dimethylurea,
  • g) compounds of the type of the acylsulfamoylbenzamides of the formula (S-IX), known from EP-A-1019368, if appropriate also in salt form,


in which

  • R101 is methyl, methoxy or trifluoromethoxy;
  • R102 is hydrogen, chlorine or methyl;
  • R103 is hydrogen, ethyl or propargyl;
  • R104 is ethyl, cyclopropyl, isopropyl or propargyl, or
  • R103 and R104 together form the group (CH2)4,
    including the stereoisomers, and the salts customary in agriculture.

Preference is given to herbicide-safener combinations comprising (A) a herbicidally effective amount of one or more compounds of the formula (I) or salts thereof and (B) an amount, acting as an antidote, of one or more safeners.

Herbicidally effective amount in the sense of the invention is an amount of one or more herbicides sufficient to have an adverse impact on plant growth. In the sense of the invention, an amount which acts as an antidote is an amount of one or more safeners sufficient to reduce the phytotoxic action of crop protection agents (for example herbicides) in crop plants.

The compounds of the formula (S-II) are known, for example, from EP-A-0 333 131 (ZA-89/1960), EP-A-0 269 806 (U.S. Pat. No. 4,891,057), EP-A-0 346 620 (AU-A-89/34951), EP-A-0 174 562, EP-A-0 346 620 (WO-A-91/08 202), WO-A-91/07 874 or WO-A 95/07 897 (ZA 94/7120) and the literature cited therein or can be prepared by or analogously to the processes described therein. The compounds of the formula (S-III) are known from EP-A-0 086 750, EP-A-0 94349 (U.S. Pat. No. 4,902,340), EP-A-0 191736 (U.S. Pat. No. 4,881,966) and EP-A-0 492 366 and the literature cited therein or can be prepared by or analogously to the processes described therein. Furthermore, some compounds are described in EP-A-0 582 198 and WO 2002/34048.

The compounds of the formula (S-IV) are known from numerous patent applications, for example U.S. Pat. Nos. 4,021,224 and 4,021,229.

Compounds of the group B (b) are furthermore known from CN-A-87/102 789, EP-A-365484 and from “The Pesticide Manual”, The British Crop Protection Council and the Royal Society of Chemistry, 11th edition, Farnham 1997.

The compounds of the group B (c) are described in WO-A-97/45016, those of group B (d) in WO-A-99/16744, those of group B (e) in EP-A-365484 and those of group B (g) in EP-A-1019368.

The publications cited contain detailed statements about preparation processes and starting materials and mention preferred compounds. These publications are expressly referred to; by reference, they form part of the present description.

Preference is given to herbicide-safener combinations comprising safeners of the formula (S-II) and/or (S-III) in which the symbols and indices are as defined below:

  • R24 is hydrogen, (C1-C18)-alkyl, (C3-C12)-cycloalkyl, (C2-C8)-alkenyl and (C2-C18)-alkynyl, where the carbon-containing groups may be substituted by one or more, preferably up to three, radicals R50;
  • R50 are identical or different and are halogen, hydroxyl, (C1-C8)-alkoxy, (C1-C8)-alkylthio, (C2-C8)-alkenylthio, (C2-C8)-alkynylthio, (C2-C8)-alkenyloxy, (C2-C8)-alkynyloxy, (C3-C7)-cycloalkyl, (C3-C7)-cycloalkoxy, cyano, mono- and di(C1-C4)-alkylamino, carboxyl, (C1-C8)-alkoxycarbonyl, (C2-C8)-alkenyloxycarbonyl, (C1-C8)-alkylthiocarbonyl, (C2-C8)-alkynyloxycarbonyl, (C1-C8)-alkylcarbonyl, (C2-C8)-alkenylcarbonyl, (C2-C8)-alkynylcarbonyl, 1-(hydroxyimino)-(C1-C8)-alkyl, 1-[(C1-C4)-alkylimino]-(C1-C4)-alkyl, 1-[(C1-C4)-alkoxyimino]-(C1-C8)-alkyl, (C1-C8)-alkylcarbonylamino, (C2-C8)-alkenylcarbonylamino, (C2-C8)-alkynylcarbonylamino, aminocarbonyl, (C1-C8)-alkylaminocarbonyl, di-(C1-C6)-alkylaminocarbonyl, (C2-C6)-alkenylaminocarbonyl, (C2-C6)-alkynylaminocarbonyl, (C1-C8)-alkoxycarbonylamino, (C1-C8)-alkylaminocarbonylamino, (C1-C6)-alkylcarbonyloxy which is unsubstituted or substituted by R51, (C2-C6)-alkenylcarbonyloxy, (C2-C6)-alkynylcarbonyloxy, (C1-C8)-alkylsulfonyl, phenyl, phenyl-(C1-C8)-alkoxy, phenyl-(C1-C6)-alkoxycarbonyl, phenoxy, phenoxy-(C1-C8)-alkoxy, phenoxy-(C1-C6)-alkoxycarbonyl, phenylcarbonyloxy, phenyl-carbonylamino, phenyl-(C1-C6)-alkylcarbonylamino, where the phenyl ring of the 9 last-mentioned radicals is unsubstituted or mono- or polysubstituted, preferably up to trisubstituted, by radicals R52; SiR′3, —O—SiR′3, R′3Si—(C1-C8)-alkoxy, —CO—O—NR′2, —O—N═CR′2, —N═CR′2, —O—NR′2, —NR′2, CH(OR′)2, —O—(CH2)m—CH(OR)2, —CR′″(OR′)2, —O—(CH2)mCR′″(OR″)2 or by R″O—CHR′″CHCOR″—(C1-C6)-alkoxy,
  • R51 are identical or different and are halogen, nitro, (C1-C4)-alkoxy and phenyl which is unsubstituted or substituted by one or more, preferably up to three, radicals R52;
  • R52 are identical or different and are halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkyl, (C1-C4)-haloalkoxy or nitro;
  • R′ are identical or different and are hydrogen, (C1-C4)-alkyl, phenyl which is unsubstituted or substituted by one or more, preferably up to three, radicals R52, or two radicals R′ together form a (C2-C6)-alkanediyl chain;
  • R″ are identical or different and are (C1-C4)-alkyl, or two radicals R″ together form a (C2-C6)-alkanediyl chain;
  • R′″ is hydrogen or (C1-C4)-alkyl;
  • m is 0, 1, 2, 3, 4, 5 or 6.

Particular preference is given to herbicide-safener combinations according to the invention comprising safeners of the formula (S-II) and/or (S-III) in which the symbols and indices are as defined below:

  • R24 is hydrogen, (C1-C8)-alkyl or (C3-C7)-cycloalkyl, where the carbon-containing radicals above are unsubstituted or mono- or polysubstituted by halogen or mono- or disubstituted, preferably monosubstituted, by radicals R50,
  • R50 are identical or different and are hydroxyl, (C1-C4)-alkoxy, carboxyl, (C1-C4)-alkoxycarbonyl, (C2-C6)-alkenyloxycarbonyl, (C2-C6)-alkynyloxycarbonyl, 1-(hydroxyimino)-(C1-C4)-alkyl, 1-[(C1-C4)-alkylimino]-(C1-C4)-alkyl and 1-[(C1-C4)-alkoxyimino]-(C1-C4)-alkyl; —SiR′3, —O—N═CR′2, —N═CR′2, —NR′2 and —O—NR′2, in which R′ are identical or different and are hydrogen, (C1-C4)-alkyl or, as a pair, are a (C4-C5)-alkanediyl chain,
  • R27, R28, R29 are identical or different and are hydrogen, (C1-C8)-alkyl, (C1-C6)-haloalkyl, (C3-C7)-cycloalkyl or phenyl which is unsubstituted or substituted by one or more radicals from the group consisting of halogen, cyano, nitro, amino, mono- and di-[(C1-C4)-alkyl]amino, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C1-C4)-alkylthio and (C1-C4)-alkylsulfonyl;
  • Rx′ is hydrogen or COOR24, where R26 is hydrogen, (C1-C8)-alkyl, (C1-C8)-haloalkyl, (C1-C4)-alkoxy-(C1-C4)-alkyl, (C1-C6)-hydroxyalkyl, (C3-C7)-cycloalkyl or tri-(C1-C4)-alkylsilyl,
  • R17, R19 are identical or different and are halogen, methyl, ethyl, methoxy, ethoxy, (C1-C2)-haloalkyl, preferably hydrogen, halogen or (C1-C2)-haloalkyl.

Very particular preference is given to safeners in which the symbols and indices in the formula (S-II) are as defined below:

  • R17 is halogen, nitro or (C1-C4)-haloalkyl;
  • n′ is 0, 1, 2 or 3;
  • R18 is a radical of the formula OR24,
  • R24 is hydrogen, (C1-C8)-alkyl or (C3-C7)-cycloalkyl, where the carbon-containing radicals above are unsubstituted or mono- or polysubstituted, preferably up to trisubstituted, by identical or different halogen radicals or up to disubstituted, preferably monosubstituted, by identical or different radicals from the group consisting of hydroxyl, (C1-C4)-alkoxy, (C1-C4)-alkoxycarbonyl, (C2-C6)-alkenyloxycarbonyl, (C2-C6)-alkynyloxycarbonyl, 1-(hydroxyimino)-(C1-C4)-alkyl, 1-[(C1-C4)-alkylimino]-(C1-C4)-alkyl, 1-[(C1-C4)-alkoxyimino]-(C1-C4)-alkyl and radicals of the formulae —SiR′3, —O—N═R′2, —N═CR′2, —NR′2 and —O—NR′2, where the radicals R′ in the formulae mentioned are identical or different and are hydrogen, (C1-C4)-alkyl or, as a pair, are (C4-C5)-alkanediyl;
  • R27, R28, R29 are identical or different and are hydrogen, (C1-C8)-alkyl, (C1-C6)-haloalkyl, (C3-C7)-cycloalkyl or phenyl which is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, nitro, (C1-C4)-haloalkyl and (C1-C4)-haloalkoxy, and
  • Rx′ is hydrogen or COOR26, where R26 is hydrogen, (C1-C8)-alkyl, (C1-C8)-haloalkyl, (C1-C4)-alkoxy-(C1-C4)-alkyl, (C1-C6)-hydroxyalkyl, (C3-C7)-cycloalkyl or tri-(C1-C4)-alkylsilyl.

Very particular preference is also given to safeners of the formula (S-III) in which the symbols and indices are as defined below:

  • R19 is halogen or (C1-C4)-haloalkyl;
  • n′ is 0, 1, 2 or 3, where (R19)n′ is preferably 5-Cl;
  • R20 is a radical of the formula OR24;
  • T is CH2 or CH(COO—((C1-C3)-alkyl)) and
  • R24 is hydrogen, (C1-C8)-alkyl, (C1-C8)-haloalkyl or (C1-C4)-alkoxy-(C1-C4)-alkyl, preferably hydrogen or (C1-C8)-alkyl.

Especially preferred are safeners of the formula (II) in which the symbols and indices are as defined below:

  • W is (W1);
  • R17 is halogen or (C1-C2)-haloalkyl;
  • n′ is 0, 1, 2 or 3, where (R17)n′ is preferably 2,4-Cl2;
  • R18 is a radical of the formula OR24;
  • R24 is hydrogen, (C1-C8)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-hydroxyalkyl, (C3-C7)-cycloalkyl, (C1-C4)-alkoxy-(C1-C4)-alkyl or tri-(C1-C2)-alkylsilyl, preferably (C1-C4)-alkyl;
  • R27 is hydrogen, (C1-C8)-alkyl, (C1-C4)-haloalkyl or (C3-C7)-cycloalkyl, preferably hydrogen or (C1-C4)-alkyl, and
  • Rx′ is COOR26, where R26 is hydrogen, (C1-C8)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-hydroxyalkyl, (C3-C7)-cycloalkyl, (C1-C4)-alkoxy-(C1-C4)-alkyl or tri-(C1-C2)-alkylsilyl, preferably hydrogen or (C1-C4)-alkyl.

Also especially preferred are herbicidal compositions comprising a safener of the formula (S-II) in which the symbols and indices are as defined below:

  • W is (W2);
  • R17 is halogen or (C1-C2)-haloalkyl;
  • n′ is 0, 1, 2 or 3, where (R17)n′ is preferably 2,4-Cl2;
  • R18 is a radical of the formula OR24;
  • R24 is hydrogen, (C1-C8)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-hydroxyalkyl, (C3-C7)-cycloalkyl, ((C1-C4)-alkoxy)-(C1-C4)-alkyl or tri-(C1-C2)-alkylsilyl, preferably (C1-C4)-alkyl;
  • R27 is hydrogen, (C1-C8)-alkyl, (C1-C4)-haloalkyl, (C3-C7)-cycloalkyl or unsubstituted or substituted phenyl, preferably hydrogen, (C1-C4)-alkyl or phenyl which is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl, nitro, cyano and (C1-C4)-alkoxy.

Especially preferred are also safeners of the formula (S-II) in which the symbols and indices are as defined below:

  • W is (W3);
  • R17 is halogen or (C1-C2)-haloalkyl;
  • n′ is 0, 1, 2 or 3, where (R17)n′ is preferably 2,4-Cl2;
  • R18 is a radical of the formula OR24;
  • R24 is hydrogen, (C1-C8)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-hydroxyalkyl, (C3-C7)-cycloalkyl, (C1-C4)-alkoxy-(C1-C4)-alkyl or tri-(C1-C2)-alkylsilyl, preferably (C1-C4)-alkyl, and
  • R28 is (C1-C8)-alkyl or (C1-C4)-haloalkyl, preferably C1-haloalkyl.

Especially preferred are also safeners of the formula (S-II) in which the symbols and indices are as defined below:

  • W is (W4);
  • R17 is halogen, nitro, (C1-C4)-alkyl, (C1-C2)-haloalkyl, preferably CF3, or (C1-C4)-alkoxy;
  • n′ is 0, 1, 2 or 3;
  • m′ is 0 or 1;
  • R18 is a radical of the formula OR24;
  • R24 is hydrogen, (C1-C4)-alkyl, carboxy-(C1-C4)-alkyl, (C1-C4)-alkoxycarbonyl-(C1-C4)-alkyl, preferably (C1-C4)-alkoxy-CO—CH2, (C1-C4)-alkoxy-CO—C(CH3)H—, HO—CO—CH2— or HO—CO—C(CH3)H , and
  • R29 is hydrogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C3-C7)-cycloalkyl or phenyl which is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl, nitro, cyano and (C1-C4)-alkoxy.

Particularly suitable as safeners for the herbicidally active compounds of the formula (I) are the following groups of compounds:

  • b) compounds of the type of the dichlorophenylpyrazoline-3-carboxylic acid (i.e. of the formula (S-II) in which W═(W1) and (R17)n′=2,4-Cl2), preferably compounds such as ethyl 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate (S-II-1, mefenpyr-diethyl), mefenpyr-dimethyl and mefenpyr (S-II-0), and related compounds as described in WO-A 91/07874;
  • c) derivatives of dichlorophenylpyrazolecarboxylic acid (i.e. of the formula (S-II) in which W═(W2) and (R17)n′=2,4-Cl2), preferably compounds such as ethyl 1-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylate (S-II-2), ethyl 1-(2,4-dichlorophenyl)-5-isopropylpyrazole-3-carboxylate (S-II-3), ethyl 1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)pyrazole-3-carboxylate (S-II-4), ethyl 1-(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate (S-II-5) and related compounds, as described in EP-A-0 333 131 and EP-A-0 269 806;
  • d) compounds of the type of the triazolecarboxylic acids (i.e. of the formula (S-II) in which W═(W3) and (R17)n′=2,4-Cl2), preferably compounds such as fenchlorazole-ethyl, i.e. ethyl 1-(2,4-dichlorophenyl)-5-trichloromethyl-(1H)-1,2,4-triazole-3-carboxylate (S-II-6), and related compounds (see EP-A-0 174 562 and EP-A-0 346 620);
  • e) compounds of the type of the 5-benzyl- or 5-phenyl-2-isoxazoline-3-carboxylic acid or of the 5,5-diphenyl-2-isoxazoline-3-carboxylic acid, such as isoxadifen (S-II -12), (in which W═(W4)), preferably compounds such as ethyl 5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylate (S-II-7) or ethyl 5-phenyl-2-isoxazoline-3-carboxylate (S-II-8) and related compounds, as described in WO-A-91/08202, or of ethyl 5,5-diphenyl-2-isoxazolinecarboxylate (S-II-9, isoxadifen-ethyl) or n-propyl 5,5-diphenyl-2-isoxazolinecarboxylate (S-II-10) or of ethyl 5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate (S-II-11), as described in WO-A-95/07897.
  • f) of the type of the 8-quinolineoxyacetic acid, for example those of the formula (S-III) in which (R19)n′=5-Cl, R20═OR24 and T=CH2, preferably the compounds
    • 1-methylhexyl (5-chloro-8-quinolineoxy)acetate (S-III-1, cloquintocet-mexyl),
    • 1,3-dimethylbut-1-yl (5-chloro-8-quinolineoxy)acetate (S-III-2),
    • 4-allyloxybutyl (5-chloro-8-quinolineoxy)acetate (S-III-3),
    • 1-allyloxyprop-2-yl (5-chloro-8-quinolineoxy)acetate (S-III-4),
    • ethyl (5-chloro-8-quinolineoxy)acetate (S-III-5),
    • methyl (5-chloro-8-quinolineoxy)acetate (S-III-6),
    • allyl (5-chloro-8-quinolineoxy)acetate (S-III-7),
    • 2-(2-propylideneiminoxy)-1-ethyl (5-chloro-8-quinolineoxy)acetate (S-III-8),
    • 2-oxoprop-1-yl(5-chloro-8-quinolineoxy)acetate (S-III-9),
    • (5-chloro-8-quinolineoxy)acetic acid (S-III-10) and its salts, as described, for example, in WO-A-2002/34048,
    • and related compounds as described in EP-A-0 860 750, EP-A-0 094 349 and EP-A-0 191 736 or EP-A-0 492 366.
  • g) Compounds of the type of the (5-chloro-8-quinolineoxy)malonic acid, i.e. of the formula (S-III) in which (R19)n′=5-Cl, R20═OR24, T=—CH(COO-alkyl)-, preferably the compounds diethyl (5-chloro-8-quinolineoxy)malonate (S-III-11), diallyl (5-chloro-8-quinolineoxy)-malonate, methyl ethyl (5-chloro-8-quinolineoxy)malonate and related compounds, as described in EP-A-0 582 198.
  • h) Compounds of the type of the dichloroacetamide, i.e. of the formula (S-IV), preferably:
    • N,N-diallyl-2,2-dichloroacetamide (dichlormid (S-IV-1), from U.S. Pat. No. 4,137,070), 4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine (IV-2, benoxacor, from EP 0 149 974),
    • N1,N2-diallyl-N2-dichloroacetylglycinamide (DKA-24 (IV-3), from HU 2143821),
    • 4-dichloroacetyl-1-oxa-4-azaspiro[4,5]decane (AD-67),
    • 2,2-dichloro-N-(1,3-dioxolan-2-ylmethyl)-N-(2-propenyl)acetamide (PPG-1292),
    • 3-dichloroacetyl-2,2,5-trimethyloxazolidine (R-29148, S-IV-4),
    • 3-dichloroacetyl-2,2-dimethyl-5-phenyloxazolidine,
    • 3-dichloroacetyl-2,2-dimethyl-5-(2-thienyl)oxazolidine,
    • 3-dichloroacetyl-5-(2-furanyl)-2,2-dimethyloxazolidine (furilazole (S-IV-5), MON 13900),
    • 1-dichloroacetylhexahydro-3,3,8a-trimethylpyrrolo[1,2-a]pyrimidin-6(2H)-one (dicyclonon, BAS 145138).
  • i) Compounds of the group B(b), preferably
    • 1,8-naphthalic anhydride (S-b-1),
    • methyl diphenylmethoxyacetate (S-b-2),
    • cyanomethoxyimino(phenyl)acetonitrile (cyometrinil) (S-b-3),
    • 1-(2-chlorobenzyl)-3-(1-methyl-1-phenylethyl)urea (cumyluron) (S-b-4),
    • O,O-diethyl S-2-ethylthioethyl phosphorodithioate (disulfoton) (S-b-5),
    • 4-chlorophenyl methylcarbamate (mephenate) (S-b-6),
    • O,O-diethyl O-phenyl phosphorothioate (dietholate) (S-b-7),
    • 4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid (CL-304415, CAS-Regno: 31541-57-8) (S-b-8),
    • 1,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile (oxabetrinil) (S-b-9),
    • 4′-chloro-2,2,2-trifluoroacetophenone O-1,3-dioxolan-2-ylmethyloxime (fluxofenim) (S-b-10),
    • 4,6-dichloro-2-phenylpyrimidine (fenclorim) (S-b-11),
    • benzyl 2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate (flurazole) (S-b-12),
    • 2-dichloromethyl-2-methyl-1,3-dioxolane (MG-191) (S-b-13),
    • N-(4-methylphenyl)-N′-(1-methyl-1-phenylethyl)urea (dymron) (S-b-14),
    • (2,4-dichlorophenoxy)acetic acid (2,4-D),
    • (4-chlorophenoxy)acetic acid,
    • (R,S)-2-(4-chloro-o-tolyloxy)propionic acid (mecoprop),
    • 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB),
    • (4-chloro-o-tolyloxy)acetic acid (MCPA),
    • 4-(4-chloro-o-tolyloxy)butyric acid,
    • 4-(4-chlorophenoxy)butyric acid,
    • 3,6-dichloro-2-methoxybenzoic acid (dicamba),
    • 1-(ethoxycarbonyl)ethyl 3,6-dichloro-2-methoxybenzoate (lactidichlor) and their salts and esters, preferably their (C1-C8)-esters.

Preferred as safeners are furthermore compounds of the formula (S-V) or salts thereof in which

  • R30 is hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, furanyl or thienyl, where each of the 4 last-mentioned radicals is unsubstituted or substituted by one or more substituents from the group consisting of halogen, (C1-C4)-alkoxy, halo-(C1-C6)-alkoxy and (C1-C4)-alkylthio and, in the case of cyclic radicals, also (C1-C4)-alkyl and (C1-C4)-haloalkyl,
  • R31 is hydrogen,
  • R32 is halogen, halo-(C1-C4)-alkyl, halo-(C1-C4)-alkoxy, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-alkylsulfonyl, (C1-C4)-alkoxycarbonyl or (C1-C4)-alkylcarbonyl, preferably halogen, (C1-C4)-haloalkyl, such as trifluoromethyl, (C1-C4)-alkoxy, halo-(C1-C4)-alkoxy, (C1-C4)-alkoxycarbonyl or (C1-C4)-alkylsulfonyl,
  • R33 is hydrogen,
  • R34 is halogen, (C1-C4)-alkyl, halo-(C1-C4)-alkyl, halo-(C1-C4)-alkoxy, (C3-C6)-cycloalkyl, phenyl, (C1-C4)-alkoxy, cyano, (C1-C4)-alkylthio, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, (C1-C4)-alkoxycarbonyl or (C1-C4)-alkylcarbonyl, preferably halogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl, such as trifluoromethyl, halo-(C1-C4)-alkoxy, (C1-C4)-alkoxy or (C1-C4)-alkylthio,
  • n is 0, 1 or 2 and
  • m is 1 or 2.

Particular preference is given to compounds of the formula (S-V) in which

  • R30═H3C—O—CH2—, R31═R33═H, R34=2-OMe (S-V-1),
  • R30═H3C—O—CH2—, R31═R33═H, R34=2-OMe-5-Cl (S-V-2),
  • R30=cyclopropyl, R31═R33═H, R34=2-OMe (S-V-3),
  • R30=cyclopropyl, R31═R33=H, R34=2-OMe-5-Cl (S-V-4),
  • R30=cyclopropyl, R31═R33=H, R34=2-Me (S-V-5),
  • R30=tert-butyl, R31═R33=H, R34=2-OMe (S-V-6).

Preference is furthermore given to safeners of the formula (S-VI) in which

  • X3 is CH;
  • R35 is hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C2-C6)-alkenyl, (C5-C6)-cycloalkenyl, phenyl or 3- to 6-membered heterocyclyl having up to three heteroatoms from the group consisting of nitrogen, oxygen and sulfur, where the six last-mentioned radicals are optionally substituted by one or more identical or different substituents from the group consisting of halogen, (C1-C6)-alkoxy, (C1-C6)-haloalkoxy, (C1-C2)-alkylsulfinyl, (C1-C2)-alkylsulfonyl, (C3-C6)-cycloalkyl, (C1-C4)-alkoxycarbonyl, (C1-C4)-alkylcarbonyl and phenyl and, in the case of cyclic radicals, also (C1-C4)-alkyl and (C1-C4)-haloalkyl;
  • R36 is hydrogen, (C1-C6)-alkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, where the three last-mentioned radicals are optionally substituted by one or more identical or different substituents from the group consisting of halogen, hydroxyl, (C1-C4)-alkyl, (C1-C4)-alkoxy and (C1-C4)-alkylthio;
  • R37 is halogen, (C1-C4)-haloalkyl, (C1-C4)-haloalkoxy, nitro, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-alkylsulfonyl, (C1-C4)-alkoxycarbonyl or (C1-C4)-alkylcarbonyl;
  • R38 is hydrogen;
  • R39 is halogen, nitro, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-haloalkoxy, (C3-C6)-cycloalkyl, phenyl, (C1-C4)-alkoxy, cyano, (C1-C4)-alkylthio, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, (C1-C4)-alkoxycarbonyl or (C1-C4)-alkylcarbonyl;
  • n is 0, 1 or 2 and
  • m is 1 or 2.

Preferred safeners of the formula (S-VII) are (S-3-1), (S-3-2), (S-3-3), (S-3-4) and (S-3-5).

Preferred safeners of the formula (VIII) are

  • 1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3-methylurea (S-VIII-1),
  • 1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylurea (S-VIII-2),
  • 1-[4-(N-4,5-dimethylbenzoylsulfamoyl)phenyl]-3-methylurea (S-VIII-3) and
  • 1-[4-(N-naphthoylsulfamoyl)phenyl]-3,3-dimethylurea (S-VIII-4),

Preferred safeners of the formula S-IX are compounds of the formulae S-IX-A1 to S-IX-A4,


from among which the compound S-IX-A3 is very particularly preferred as safener.

Particularly preferred combinations of herbicidally active compounds of the formula (I) as listed in any of Tables 1 to 4 and safeners (B) are those in which the safener (B) is selected from the group of safeners consisting of the compounds of the formulae S-II-1 (mefenpyr-diethyl), S-II-9 (isoxadifen-ethyl), S-III-1 (chloquintocet-mexyl), S-b-11 (fenclorim), S-b-14 (dymron), S-IX-A3 (4-cyclopropylaminocarbonyl-N-(2-methoxybenzoyl)benzenesulfonamide [N-({4-[(cyclopropylamino)carbonyl]phenyl}-sulfonyl)-2-methoxybenzamide], very particularly preferred as safeners (B) are the compounds S-II-1 and S-IX-A3).

Particularly preferred for use in rice is isoxadifen-ethyl. Particularly preferred for use in cereals are mefenpyr-diethyl, cloquintocet-mexyl and 4-cyclopropylaminocarbonyl-N-(2-methoxybenzoyl)benzenesulfonamide [N-({4-[(cyclopropylamino)carbonyl]phenyl}sulfonyl)-2-methoxybenzamide], in corn in particular isoxadifen-ethyl and 4-cyclopropylaminocarbonyl-N-(2-methoxybenzoyl)-benzenesulfonamide [N-({4-[(cyclopropylamino)carbonyl]phenyl}sulfonyl)-2-methoxybenzamide]. For use in sugar cane, preference is given to isoxadifen-ethyl. A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, is also possible.

Some of the safeners are already known as herbicides and accordingly, in addition to the herbicidal action against harmful plants, also act by protecting the crop plants.

The weight ratios of herbicide (mixture) to safener generally depend on the herbicide application rate and the effectiveness of the safener in question and may vary within wide limits, for example in the range from 200:1 to 1:200, preferably from 100:1 to 1:100, in particular from 20:1 to 1:20. The safeners may be formulated analogously to the compounds of the formula (I) or their mixtures with other herbicides/pesticides and be provided and used as a finished formulation or as a tank mix with the herbicides.

For application, the formulations present in commercial form are, if appropriate, diluted in a customary manner, for example in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules with water. Preparations in the form of dusts, granules for soil application or granules for broadcasting and sprayable solutions are usually not diluted with other inert substances prior to application.

The application rate of the compounds of the formula (I) varies according to the external conditions such as, inter alia, temperature, humidity and the type of herbicide used. It may vary within wide limits, for example between 0.001 and 10.0 kg/ha or more of active substance; however, preferably it is between 0.005 and 5 kg/ha.

The present invention is illustrated in more detail by the examples below; however, these examples do not limit the invention in any way.

 A. SYNTHESIS EXAMPLES

Some examples of syntheses of compounds of the formula (I) or salts thereof are described in an exemplary manner below.

5-Bromo-2-[(S)-{[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-1,3-thiazole (Ex. 2637) and 5-bromo-2-[(R)-{[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-1,3-thiazole (Ex. 3725)

The starting material [5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl imidothiocarbamate hydrobromide is obtained by mixing equimolar amounts of 4-(bromomethyl)-5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazole and thiourea in ethanol and heating under reflux for 8 hours, concentrating the resulting mixture and recrystallizing from tetrahydrofuran.

[5-(Difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl imidothiocarbamate hydrobromide (7.928 g, 21 mmol) is added to a mixture, stirred vigorously, of 100 ml of toluene and 50% strength aqueous sodium hydroxide solution (50 g), and the mixture is stirred vigorously for another 1.5 hours. Tetra-n-butylammonium bromide (1.858 g, 6 mmol) and 2,5-dibromo-1,3-thiazole (5.0 g, 21 mmol) are then added, and the mixture is stirred at 25° C. for a further 5 hours and then allowed to stand overnight. For work-up, the reaction solution is added to water and extracted with toluene. The combined organic phases are dried and concentrated. For purification, the product is chromatographed on silica gel (heptane/ethyl acetate, gradient). This gives 5.62 g of product (61.1% of theory).

NMR (CDCl3, 400 MHz): 3.8 (s, 3H, CH3); 4.31 (s, 2H, SCH2); 6.69 (t, 1H, OCHF2); 7.58 (s, 1H, thiazolyl-H).

The 5-bromo-2-({[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfanyl)-1,3-thiazole obtained in this manner (4.0 g, 9.429 mmol) is initially charged in 100 ml of toluene. With stirring, 3-chloroperbenzoic acid (1.976 g, 8.015 mmol, 77% pure) is then added a little at a time, and the mixture is stirred at room temperature for a further 4 hours. For work-up, the reaction mixture is washed successively with water, aqueous NaHSO3 solution, aqueous NaHCO3 solution and finally with NaCl solution. The organic phase is dried over magnesium sulfate, filtered off and concentrated. The residue is triturated with n-heptane, filtered off and dried. The racemic 5-bromo-2-({[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl)-1,3-thiazole obtained (3.75 g) is purified by preparative chiral HPLC (column: Chiralcel® OD; mobile phase: n-hexane/2-propanol 90:10; flow rate: 0.6 ml/min; column temperature: 25° C.) and separated into the enantiomers. This gives 1.505 g (36.2% of theory) of 5-bromo-2-[(S)-{[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-1,3-thiazole (Rt=10.258 min) and 1.305 g (31.4% of theory) of 5-bromo-2-[(R)-{[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-1,3-thiazole (Rt=12.557 min).

The absolute configuration of 5-bromo-2-[(S)-{[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-1,3-thiazole was confirmed by X-ray analysis.

5-Bromo-2-[(S)-{[5-chloro-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-1,3-thiazole (Ex. 2632) and 5-bromo-2-[(R)-{[5-chloro-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-1,3-thiazole (Ex. 3720)

Molecular sieve 4 A (0.610 g) is initially charged in dichloromethane (5 ml). The catalyst titanium(IV) isopropoxide (0.18 ml, 0.62 mmol) and the ligand (R)-(−)-mandelic acid (0.142 g, 0.93 mmol) are added. The mixture is stirred at room temperature for a further 30 minutes. 5-Bromo-2-({[5-chloro-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}-sulfanyl)-1,3-thiazole, which can be obtained according to WO 2006/123088, is then added (0.610 g, 1.55 mmol). The mixture is stirred at room temperature for a further hour, during which time the catalyst/ligand complex forms. Cumene hydroperoxide is then added dropwise (0.29 ml, 80%, 1.55 mmol). The mixture is then stirred at room temperature for a further seven hours and stored in a fridge (−5° C.) for one week. For work-up, the reaction mixture is washed successively with water, twice with aqueous 2M NaOH solution and finally with NaCl solution. The organic phase is dried over magnesium sulfate, filtered off and concentrated. The crude product obtained contains 5-bromo-2-[{[5-chloro-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-1,3-thiazole and the corresponding sulfone (0.3 g, about 1:1) and is purified by preparative HPLC. This gives 0.116 g (18.2% of theory) of 5-bromo-2-[{[5-chloro-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-1,3-thiazole with 11% ee (S), which is separated into the enantiomers by preparative chiral HPLC. This gives 0.063 g (10% of theory) of 5-bromo-2-[(S)-{[5-chloro-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-1,3-thiazole (Rt=18.600 min) and 0.042 g (7% of theory) of 5-bromo-2-[(R)-{[5-chloro-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-1,3-thiazole (Rt=22.652 min).

5-Bromo-2-[(S)-(2,6-difluorobenzyl)sulfinyl]-1,3-thiazole (Ex. 259) and 5-bromo-2-[(R)-(2,6-difluorobenzyl)sulfinyl]-1,3-thiazole (Ex. 1449)

a) Preparation of 5-bromo-2-[(2,6-difluorobenzyl)sulfanyl]-1,3-thiazole

The starting material 2,6-difluorobenzyl imidothiocarbamate hydrochloride is obtained by mixing equimolar amounts of 2,6-difluorobenzyl chloride and thiourea in ethanol, heating under reflux for 8 hours, concentrating and recrystallizing from tetrahydrofuran.

2,6-Difluorobenzyl imidothiocarbamate hydrochloride (1.972 g, 8 mmol) is added to a vigorously stirred mixture consisting of 50 ml of toluene and 50% strength aqueous sodium hydroxide solution (28 g), and the mixture is stirred vigorously for a further 1.5 hours. Tetra-n-butylammonium bromide (0.746 g, 2 mmol) and 5-bromo-2-(methylsulfonyl)-1,3-thiazole (2.0 g, 8 mmol) are added, and the mixture is stirred at 25° C. for a further 6 hours and allowed to stand overnight. For work-up, the reaction solution is added to water and extracted with toluene. The combined organic phases are dried and concentrated. For purification, the product is chromatographed on silica gel (heptane/ethyl acetate, gradient). This gives 1.7 g of product (60.6% of theory).

NMR (CDCl3, 400 MHz): 4.42 (s, 2H, SCH2); 6.89 (m, 2H, Ar); 7.24 (m, 1H, Ar); 7.61 (s, 1H, thiazolyl-H).

b) Asymmetric Sulfoxidation

The ligand (R,R)-1,2-diphenylethane-1,2-diol [(R,R)-(+)-hydrobenzoin, 0.033 g, 0.15 mmol] is initially charged in CCl4 (10 ml). The catalyst titanium(IV) isopropoxide (0.02 ml, 0.077 mmol) is added, and water (0.028 ml, 1.55 mmol) is then added dropwise. The mixture is stirred at room temperature for 15 minutes. 5-Bromo-2-[(2,6-difluorobenzyl)sulfanyl]-1,3-thiazole (0.5 g, 1.55 mmol) is then added, and the mixture is stirred at room temperature for a further 15 minutes. With ice-bath cooling, tert-butyl hydroperoxide (TBHP, 70% strength in water, 0.44 ml, 3 mmol) is then added dropwise. The mixture is stirred for a further two hours and then allowed to thaw overnight. For work-up, the reaction mixture is diluted with dichloromethane and washed successively with water, twice with 5% strength Na2S2O5 solution and finally with NaCl solution. The organic phase is dried over magnesium sulfate, filtered off and concentrated. The residue is chromatographed on silica gel (heptane/ethyl acetate 10:0 to 7:3). The mixture obtained (0.120 g) comprises 5-bromo-2-[(S)-(2,6-difluorobenzyl)sulfinyl]-1,3-thiazole with 23% ee (S) and the corresponding sulfone and is directly separated into the enantiomers by preparative chiral HPLC. This gives 0.032 g (6% of theory) of 5-bromo-2-[(S)-(2,6-difluorobenzyl)sulfinyl]-1,3-thiazole (Rt=17.053 min) and 0.032 g (6% of theory) of 5-bromo-2-[(R)-(2,6-difluorobenzyl)sulfinyl]-1,3-thiazole (Rt=19.430 min).

Retention times (Rt, in minutes) and enantiomeric excess (ee) of chiral compounds are determined by analytic chiral HPLC [Chiralcel® OD column (250×4.6 mm, particle size 5 μm), temperature 25° C., flow rate 0.6 ml/min, hexane/2-propanol 90:10 v/v].

The racemates or enantiomeric mixtures are separated into the respective enantiomers by preparative chiral HPLC [Chiralcel® OD column (250×5 mm, particle size 10 μm), temperature 25° C., flow rate 0.6 ml/min, hexane/2-propanol 90:10 v/v].

The compounds described in Tables 1-4 below are obtained according to or analogously to the synthesis examples described above.

In the tables:

  • Me=methyl
  • Et=ethyl
  • Ph=phenyl
  • Pr=n-propyl
  • cPr=cyclopropyl
  • iPr=isopropyl
  • Bu=n-butyl
  • cBu=cyclobutyl
  • iBu=isobutyl
  • sBu=sec-butyl
  • tBu=tert-butyl
  • cPen=cyclopentyl
  • cHex=cyclohexyl

TABLE 1 Compounds of the formula Ia-S (Ia-S) Ex. No. R11 R12 R1 R2 R3 R4 R5 1. H H H H H H H 2. H H F H H H H 3. H H F H H F H 4. H H F H H H F 5. H H F Me H H F 6. H H F H H H Cl 7. H H CF3 H H H H 8. H H Me H H H H 9. H H F H H H CF3 10. H H F CF3 H H F 11. H H Br H H H H 12. H H I H H H H 13. H H Cl H H H H 14. H H Cl H Cl H H 15. H H Cl H H H Cl 16. H H H Cl Cl H H 17. H H Cl Cl Cl H H 18. H H Cl Cl H Cl H 19. H H Cl Cl Cl H Cl 20. H H Cl Cl Cl Cl H 21. H H Cl Cl Cl Cl Cl 22. H H Cl Cl H H Cl 23. H H Cl H Cl Cl H 24. H H Cl H H Cl Cl 25. H H H Cl Cl Cl H 26. H H NO2 H H H H 27. H H H Cl H H H 28. H H H H Cl H H 29. H H Cl H Cl H Cl 30. H H Cl Cl H H H 31. H H Cl H H Cl H 32. H H H Cl H Cl H 33. H H H OMe H H H 34. H H C(O)OMe H H H H 35. H H F Cl H H H 36. H H F Me H H H 37. H H H Me H H H 38. H H OMe H H H H 39. H H F F F H H 40. H H F F H F H 41. H H H F F F H 42. H H F H F F H 43. H H Me H Me H H 44. H H Me H H Me H 45. H H F H H CF3 H 46. H H F H Br H H 47. H H Me Me H H H 48. H H F F F F F 49. H H F H H H OMe 50. H H Cl H F H H 51. H H NO2 H Cl H H 52. H H NO2 H H Me H 53. H H F H H H I 54. H H F H H H Br 55. H H Br H H H Br 56. H H Cl H H H Me 57. H H Cl H H H OCHF2 58. H H Cl H H H OMe 59. H H Me H H H OMe 60. H H OEt H H H CF3 61. H H OC(O)Me H H H H 62. H H OEt H H H Me 63. H H Me Me H H Me 64. H H Cl H H H C(O)OMe 65. H H Cl H H OMe H 66. H H F F H F F 67. H H Cl H H F H 68. H H F H H F Cl 69. H H F H H Cl H 70. H H Cl H H CF3 H 71. H H Cl Me H H H 72. H H OCHF2 H H H H 73. H H OCH2CF3 H H H H 74. H H CF3 H H H OCHF2 75. H H CF3 H H H OCH2CF3 76. H H Me H H H Me 77. H H Cl H H H F 78. H H F H F H H 79. H H F Me H H Cl 80. H H F H H OMe H 81. H H Cl H OCH2O H 82. H H Me H H F H 83. H H OCF3 H H H H 84. H H F F H H H 85. H H OMe H H Cl H 86. F H H H H H H 87. F H F H H H H 88. F H F H H F H 89. F H F H H H F 90. F H F Me H H F 91. F H F H H H Cl 92. F H CF3 H H H H 93. F H Me H H H H 94. F H F H H H CF3 95. F H F CF3 H H F 96. F H Br H H H H 97. F H I H H H H 98. F H Cl H H H H 99. F H Cl H Cl H H 100. F H Cl H H H Cl 101. F H H Cl Cl H H 102. F H Cl Cl Cl H H 103. F H Cl Cl H Cl H 104. F H Cl Cl Cl H Cl 105. F H Cl Cl Cl Cl H 106. F H Cl Cl Cl Cl Cl 107. F H Cl Cl H H Cl 108. F H Cl H Cl Cl H 109. F H Cl H H Cl Cl 110. F H H Cl Cl Cl H 111. F H NO2 H H H H 112. F H H Cl H H H 113. F H H H Cl H H 114. F H Cl H Cl H Cl 115. F H Cl Cl H H H 116. F H Cl H H Cl H 117. F H H Cl H Cl H 118. F H H OMe H H H 119. F H C(O)OMe H H H H 120. F H F Cl H H H 121. F H F Me H H H 122. F H H Me H H H 123. F H OMe H H H H 124. F H F F F H H 125. F H F F H F H 126. F H H F F F H 127. F H F H F F H 128. F H Me H Me H H 129. F H Me H H Me H 130. F H F H H CF3 H 131. F H F H Br H H 132. F H Me Me H H H 133. F H F F F F F 134. F H F H H H OMe 135. F H Cl H F H H 136. F H NO2 H Cl H H 137. F H NO2 H H Me H 138. F H F H H H I 139. F H F H H H Br 140. F H Br H H H Br 141. F H Cl H H H Me 142. F H Cl H H H OCHF2 143. F H Cl H H H OMe 144. F H Me H H H OMe 145. F H OEt H H H CF3 146. F H OC(O)Me H H H H 147. F H OEt H H H Me 148. F H Me Me H H Me 149. F H Cl H H H C(O)OMe 150. F H Cl H H OMe H 151. F H F F H F F 152. F H Cl H H F H 153. F H F H H F Cl 154. F H F H H Cl H 155. F H Cl H H CF3 H 156. F H Cl Me H H H 157. F H OCHF2 H H H H 158. F H OCH2CF3 H H H H 159. F H CF3 H H H OCHF2 160. F H CF3 H H H OCH2CF3 161. F H Me H H H Me 162. F H Cl H H H F 163. F H F H F H H 164. F H F Me H H Cl 165. F H F H H OMe H 166. F H Cl H OCH2O H 167. F H Me H H F H 168. F H OCF3 H H H H 169. F H F F H H H 170. F H OMe H H Cl H 171. Cl H H H H H H 172. Cl H F H H H H 173. Cl H F H H F H 174. Cl H F H H H F 175. Cl H F Me H H F 176. Cl H F H H H Cl 177. Cl H CF3 H H H H 178. Cl H Me H H H H 179. Cl H F H H H CF3 180. Cl H F CF3 H H F 181. Cl H Br H H H H 182. Cl H I H H H H 183. Cl H Cl H H H H 184. Cl H Cl H Cl H H 185. Cl H Cl H H H Cl 186. Cl H H Cl Cl H H 187. Cl H Cl Cl Cl H H 188. Cl H Cl Cl H Cl H 189. Cl H Cl Cl Cl H Cl 190. Cl H Cl Cl Cl Cl H 191. Cl H Cl Cl Cl Cl Cl 192. Cl H Cl Cl H H Cl 193. Cl H Cl H Cl Cl H 194. Cl H Cl H H Cl Cl 195. Cl H H Cl Cl Cl H 196. Cl H NO2 H H H H 197. Cl H H Cl H H H 198. Cl H H H Cl H H 199. Cl H Cl H Cl H Cl 200. Cl H Cl Cl H H H 201. Cl H Cl H H Cl H 202. Cl H H Cl H Cl H 203. Cl H H OMe H H H 204. Cl H C(O)OMe H H H H 205. Cl H F Cl H H H 206. Cl H F Me H H H 207. Cl H H Me H H H 208. Cl H OMe H H H H 209. Cl H F F F H H 210. Cl H F F H F H 211. Cl H H F F F H 212. Cl H F H F F H 213. Cl H Me H Me H H 214. Cl H Me H H Me H 215. Cl H F H H CF3 H 216. Cl H F H Br H H 217. Cl H Me Me H H H 218. Cl H F F F F F 219. Cl H F H H H OMe 220. Cl H Cl H F H H 221. Cl H NO2 H Cl H H 222. Cl H NO2 H H Me H 223. Cl H F H H H I 224. Cl H F H H H Br 225. Cl H Br H H H Br 226. Cl H Cl H H H Me 227. Cl H Cl H H H OCHF2 228. Cl H Cl H H H OMe 229. Cl H Me H H H OMe 230. Cl H OEt H H H CF3 231. Cl H OC(O)Me H H H H 232. Cl H OEt H H H Me 233. Cl H Me Me H H Me 234. Cl H Cl H H H C(O)OMe 235. Cl H Cl H H OMe H 236. Cl H F F H F F 237. Cl H Cl H H F H 238. Cl H F H H F Cl 239. Cl H F H H Cl H 240. Cl H Cl H H CF3 H 241. Cl H Cl Me H H H 242. Cl H OCHF2 H H H H 243. Cl H OCH2CF3 H H H H 244. Cl H CF3 H H H OCHF2 245. Cl H CF3 H H H OCH2CF3 246. Cl H Me H H H Me 247. Cl H Cl H H H F 248. Cl H F H F H H 249. Cl H F Me H H Cl 250. Cl H F H H OMe H 251. Cl H Cl H OCH2O H 252. Cl H Me H H F H 253. Cl H OCF3 H H H H 254. Cl H F F H H H 255. Cl H OMe H H Cl H 256. Br H H H H H H 257. Br H F H H H H 258. Br H F H H F H 259. Br H F H H H F 260. Br H F Me H H F 261. Br H F H H H Cl 262. Br H CF3 H H H H 263. Br H Me H H H H 264. Br H F H H H CF3 265. Br H F CF3 H H F 266. Br H Br H H H H 267. Br H I H H H H 268. Br H Cl H H H H 269. Br H Cl H Cl H H 270. Br H Cl H H H Cl 271. Br H H Cl Cl H H 272. Br H Cl Cl Cl H H 273. Br H Cl Cl H Cl H 274. Br H Cl Cl Cl H Cl 275. Br H Cl Cl Cl Cl H 276. Br H Cl Cl Cl Cl Cl 277. Br H Cl Cl H H Cl 278. Br H Cl H Cl Cl H 279. Br H Cl H H Cl Cl 280. Br H H Cl Cl Cl H 281. Br H NO2 H H H H 282. Br H H Cl H H H 283. Br H H H Cl H H 284. Br H Cl H Cl H Cl 285. Br H Cl Cl H H H 286. Br H Cl H H Cl H 287. Br H H Cl H Cl H 288. Br H H OMe H H H 289. Br H C(O)OMe H H H H 290. Br H F Cl H H H 291. Br H F Me H H H 292. Br H H Me H H H 293. Br H OMe H H H H 294. Br H F F F H H 295. Br H F F H F H 296. Br H H F F F H 297. Br H F H F F H 298. Br H Me H Me H H 299. Br H Me H H Me H 300. Br H F H H CF3 H 301. Br H F H Br H H 302. Br H Me Me H H H 303. Br H F F F F F 304. Br H F H H H OMe 305. Br H Cl H F H H 306. Br H NO2 H Cl H H 307. Br H NO2 H H Me H 308. Br H F H H H I 309. Br H F H H H Br 310. Br H Br H H H Br 311. Br H Cl H H H Me 312. Br H Cl H H H OCHF2 313. Br H Cl H H H OMe 314. Br H Me H H H OMe 315. Br H OEt H H H CF3 316. Br H OC(O)Me H H H H 317. Br H OEt H H H Me 318. Br H Me Me H H Me 319. Br H Cl H H H C(O)OMe 320. Br H Cl H H OMe H 321. Br H F F H F F 322. Br H Cl H H F H 323. Br H F H H F Cl 324. Br H F H H Cl H 325. Br H Cl H H CF3 H 326. Br H Cl Me H H H 327. Br H OCHF2 H H H H 328. Br H OCH2CF3 H H H H 329. Br H CF3 H H H OCHF2 330. Br H CF3 H H H OCH2CF3 331. Br H Me H H H Me 332. Br H Cl H H H F 333. Br H F H F H H 334. Br H F Me H H Cl 335. Br H F H H OMe H 336. Br H Cl H OCH2O H 337. Br H Me H H F H 338. Br H OCF3 H H H H 339. Br H F F H H H 340. Br H OMe H H Cl H 341. I H H H H H H 342. I H F H H H H 343. I H F H H F H 344. I H F H H H F 345. I H F Me H H F 346. I H F H H H Cl 347. I H CF3 H H H H 348. I H Me H H H H 349. I H F H H H CF3 350. I H F CF3 H H F 351. I H Br H H H H 352. I H I H H H H 353. I H Cl H H H H 354. I H Cl H Cl H H 355. I H Cl H H H Cl 356. I H H Cl Cl H H 357. I H Cl Cl Cl H H 358. I H Cl Cl H Cl H 359. I H Cl Cl Cl H Cl 360. I H Cl Cl Cl Cl H 361. I H Cl Cl Cl Cl Cl 362. I H Cl Cl H H Cl 363. I H Cl H Cl Cl H 364. I H Cl H H Cl Cl 365. I H H Cl Cl Cl H 366. I H NO2 H H H H 367. I H H Cl H H H 368. I H H H Cl H H 369. I H Cl H Cl H Cl 370. I H Cl Cl H H H 371. I H Cl H H Cl H 372. I H H Cl H Cl H 373. I H H OMe H H H 374. I H C(O)OMe H H H H 375. I H F Cl H H H 376. I H F Me H H H 377. I H H Me H H H 378. I H OMe H H H H 379. I H F F F H H 380. I H F F H F H 381. I H H F F F H 382. I H F H F F H 383. I H Me H Me H H 384. I H Me H H Me H 385. I H F H H CF3 H 386. I H F H Br H H 387. I H Me Me H H H 388. I H F F F F F 389. I H F H H H OMe 390. I H Cl H F H H 391. I H NO2 H Cl H H 392. I H NO2 H H Me H 393. I H F H H H I 394. I H F H H H Br 395. I H Br H H H Br 396. I H Cl H H H Me 397. I H Cl H H H OCHF2 398. I H Cl H H H OMe 399. I H Me H H H OMe 400. I H OEt H H H CF3 401. I H OC(O)Me H H H H 402. I H OEt H H H Me 403. I H Me Me H H Me 404. I H Cl H H H C(O)OMe 405. I H Cl H H OMe H 406. I H F F H F F 407. I H Cl H H F H 408. I H F H H F Cl 409. I H F H H Cl H 410. I H Cl H H CF3 H 411. I H Cl Me H H H 412. I H OCHF2 H H H H 413. I H OCH2CF3 H H H H 414. I H CF3 H H H OCHF2 415. I H CF3 H H H OCH2CF3 416. I H Me H H H Me 417. I H Cl H H H F 418. I H F H F H H 419. I H F Me H H Cl 420. I H F H H OMe H 421. I H Cl H OCH2O H 422. I H Me H H F H 423. I H OCF3 H H H H 424. I H F F H H H 425. I H OMe H H Cl H 426. H Cl H H H H H 427. H Cl F H H H H 428. H Cl F H H F H 429. H Cl F H H H F 430. H Cl F Me H H F 431. H Cl F H H H Cl 432. H Cl CF3 H H H H 433. H Cl Me H H H H 434. H Cl F H H H CF3 435. H Cl F CF3 H H F 436. H Cl Br H H H H 437. H Cl I H H H H 438. H Cl Cl H H H H 439. H Cl Cl H Cl H H 440. H Cl Cl H H H Cl 441. H Cl H Cl Cl H H 442. H Cl Cl Cl Cl H H 443. H Cl Cl Cl H Cl H 444. H Cl Cl Cl Cl H Cl 445. H Cl Cl Cl Cl Cl H 446. H Cl Cl Cl Cl Cl Cl 447. H Cl Cl Cl H H Cl 448. H Cl Cl H Cl Cl H 449. H Cl Cl H H Cl Cl 450. H Cl H Cl Cl Cl H 451. H Cl NO2 H H H H 452. H Cl H Cl H H H 453. H Cl H H Cl H H 454. H Cl Cl H Cl H Cl 455. H Cl Cl Cl H H H 456. H Cl Cl H H Cl H 457. H Cl H Cl H Cl H 458. H Cl H OMe H H H 459. H Cl C(O)OMe H H H H 460. H Cl F Cl H H H 461. H Cl F Me H H H 462. H Cl H Me H H H 463. H Cl OMe H H H H 464. H Cl F F F H H 465. H Cl F F H F H 466. H Cl H F F F H 467. H Cl F H F F H 468. H Cl Me H Me H H 469. H Cl Me H H Me H 470. H Cl F H H CF3 H 471. H Cl F H Br H H 472. H Cl Me Me H H H 473. H Cl F F F F F 474. H Cl F H H H OMe 475. H Cl Cl H F H H 476. H Cl NO2 H Cl H H 477. H Cl NO2 H H Me H 478. H Cl F H H H I 479. H Cl F H H H Br 480. H Cl Br H H H Br 481. H Cl Cl H H H Me 482. H Cl Cl H H H OCHF2 483. H Cl Cl H H H OMe 484. H Cl Me H H H OMe 485. H Cl OEt H H H CF3 486. H Cl OC(O)Me H H H H 487. H Cl OEt H H H Me 488. H Cl Me Me H H Me 489. H Cl Cl H H H C(O)OMe 490. H Cl Cl H H OMe H 491. H Cl F F H F F 492. H Cl Cl H H F H 493. H Cl F H H F Cl 494. H Cl F H H Cl H 495. H Cl Cl H H CF3 H 496. H Cl Cl Me H H H 497. H Cl OCHF2 H H H H 498. H Cl OCH2CF3 H H H H 499. H Cl CF3 H H H OCHF2 500. H Cl CF3 H H H OCH2CF3 501. H Cl Me H H H Me 502. H Cl Cl H H H F 503. H Cl F H F H H 504. H Cl F Me H H Cl 505. H Cl F H H OMe H 506. H Cl Cl H OCH2O H 507. H Cl Me H H F H 508. H Cl OCF3 H H H H 509. H Cl F F H H H 510. H Cl OMe H H Cl H 511. H Br H H H H H 512. H Br F H H H H 513. H Br F H H F H 514. H Br F H H H F 515. H Br F Me H H F 516. H Br F H H H Cl 517. H Br CF3 H H H H 518. H Br Me H H H H 519. H Br F H H H CF3 520. H Br F CF3 H H F 521. H Br Br H H H H 522. H Br I H H H H 523. H Br Cl H H H H 524. H Br Cl H Cl H H 525. H Br Cl H H H Cl 526. H Br H Cl Cl H H 527. H Br Cl Cl Cl H H 528. H Br Cl Cl H Cl H 529. H Br Cl Cl Cl H Cl 530. H Br Cl Cl Cl Cl H 531. H Br Cl Cl Cl Cl Cl 532. H Br Cl Cl H H Cl 533. H Br Cl H Cl Cl H 534. H Br Cl H H Cl Cl 535. H Br H Cl Cl Cl H 536. H Br NO2 H H H H 537. H Br H Cl H H H 538. H Br H H Cl H H 539. H Br Cl H Cl H Cl 540. H Br Cl Cl H H H 541. H Br Cl H H Cl H 542. H Br H Cl H Cl H 543. H Br H OMe H H H 544. H Br C(O)OMe H H H H 545. H Br F Cl H H H 546. H Br F Me H H H 547. H Br H Me H H H 548. H Br OMe H H H H 549. H Br F F F H H 550. H Br F F H F H 551. H Br H F F F H 552. H Br F H F F H 553. H Br Me H Me H H 554. H Br Me H H Me H 555. H Br F H H CF3 H 556. H Br F H Br H H 557. H Br Me Me H H H 558. H Br F F F F F 559. H Br F H H H OMe 560. H Br Cl H F H H 561. H Br NO2 H Cl H H 562. H Br NO2 H H Me H 563. H Br F H H H I 564. H Br F H H H Br 565. H Br Br H H H Br 566. H Br Cl H H H Me 567. H Br Cl H H H OCHF2 568. H Br Cl H H H OMe 569. H Br Me H H H OMe 570. H Br OEt H H H CF3 571. H Br OC(O)Me H H H H 572. H Br OEt H H H Me 573. H Br Me Me H H Me 574. H Br Cl H H H C(O)OMe 575. H Br Cl H H OMe H 576. H Br F F H F F 577. H Br Cl H H F H 578. H Br F H H F Cl 579. H Br F H H Cl H 580. H Br Cl H H CF3 H 581. H Br Cl Me H H H 582. H Br OCHF2 H H H H 583. H Br OCH2CF3 H H H H 584. H Br CF3 H H H OCHF2 585. H Br CF3 H H H OCH2CF3 586. H Br Me H H H Me 587. H Br Cl H H H F 588. H Br F H F H H 589. H Br F Me H H Cl 590. H Br F H H OMe H 591. H Br Cl H OCH2O H 592. H Br Me H H F H 593. H Br OCF3 H H H H 594. H Br F F H H H 595. H Br OMe H H Cl H 596. Me H H H H H H 597. Me H F H H H H 598. Me H F H H F H 599. Me H F H H H F 600. Me H F Me H H F 601. Me H F H H H Cl 602. Me H CF3 H H H H 603. Me H Me H H H H 604. Me H F H H H CF3 605. Me H F CF3 H H F 606. Me H Br H H H H 607. Me H I H H H H 608. Me H Cl H H H H 609. Me H Cl H Cl H H 610. Me H Cl H H H Cl 611. Me H H Cl Cl H H 612. Me H Cl Cl Cl H H 613. Me H Cl Cl H Cl H 614. Me H Cl Cl Cl H Cl 615. Me H Cl Cl Cl Cl H 616. Me H Cl Cl Cl Cl Cl 617. Me H Cl Cl H H Cl 618. Me H Cl H Cl Cl H 619. Me H Cl H H Cl Cl 620. Me H H Cl Cl Cl H 621. Me H NO2 H H H H 622. Me H H Cl H H H 623. Me H H H Cl H H 624. Me H Cl H Cl H Cl 625. Me H Cl Cl H H H 626. Me H Cl H H Cl H 627. Me H H Cl H Cl H 628. Me H H OMe H H H 629. Me H C(O)OMe H H H H 630. Me H F Cl H H H 631. Me H F Me H H H 632. Me H H Me H H H 633. Me H OMe H H H H 634. Me H F F F H H 635. Me H F F H F H 636. Me H H F F F H 637. Me H F H F F H 638. Me H Me H Me H H 639. Me H Me H H Me H 640. Me H F H H CF3 H 641. Me H F H Br H H 642. Me H Me Me H H H 643. Me H F F F F F 644. Me H F H H H OMe 645. Me H Cl H F H H 646. Me H NO2 H Cl H H 647. Me H NO2 H H Me H 648. Me H F H H H I 649. Me H F H H H Br 650. Me H Br H H H Br 651. Me H Cl H H H Me 652. Me H Cl H H H OCHF2 653. Me H Cl H H H OMe 654. Me H Me H H H OMe 655. Me H OEt H H H CF3 656. Me H OC(O)Me H H H H 657. Me H OEt H H H Me 658. Me H Me Me H H Me 659. Me H Cl H H H C(O)OMe 660. Me H Cl H H OMe H 661. Me H F F H F F 662. Me H Cl H H F H 663. Me H F H H F Cl 664. Me H F H H Cl H 665. Me H Cl H H CF3 H 666. Me H Cl Me H H H 667. Me H OCHF2 H H H H 668. Me H OCH2CF3 H H H H 669. Me H CF3 H H H OCHF2 670. Me H CF3 H H H OCH2CF3 671. Me H Me H H H Me 672. Me H Cl H H H F 673. Me H F H F H H 674. Me H F Me H H Cl 675. Me H F H H OMe H 676. Me H Cl H OCH2O H 677. Me H Me H H F H 678. Me H OCF3 H H H H 679. Me H F F H H H 680. Me H OMe H H Cl H 681. H Me H H H H H 682. H Me F H H H H 683. H Me F H H F H 684. H Me F H H H F 685. H Me F Me H H F 686. H Me F H H H Cl 687. H Me CF3 H H H H 688. H Me Me H H H H 689. H Me F H H H CF3 690. H Me F CF3 H H F 691. H Me Br H H H H 692. H Me I H H H H 693. H Me Cl H H H H 694. H Me Cl H Cl H H 695. H Me Cl H H H Cl 696. H Me H Cl Cl H H 697. H Me Cl Cl Cl H H 698. H Me Cl Cl H Cl H 699. H Me Cl Cl Cl H Cl 700. H Me Cl Cl Cl Cl H 701. H Me Cl Cl Cl Cl Cl 702. H Me Cl Cl H H Cl 703. H Me Cl H Cl Cl H 704. H Me Cl H H Cl Cl 705. H Me H Cl Cl Cl H 706. H Me NO2 H H H H 707. H Me H Cl H H H 708. H Me H H Cl H H 709. H Me Cl H Cl H Cl 710. H Me Cl Cl H H H 711. H Me Cl H H Cl H 712. H Me H Cl H Cl H 713. H Me H OMe H H H 714. H Me C(O)OMe H H H H 715. H Me F Cl H H H 716. H Me F Me H H H 717. H Me H Me H H H 718. H Me OMe H H H H 719. H Me F F F H H 720. H Me F F H F H 721. H Me H F F F H 722. H Me F H F F H 723. H Me Me H Me H H 724. H Me Me H H Me H 725. H Me F H H CF3 H 726. H Me F H Br H H 727. H Me Me Me H H H 728. H Me F F F F F 729. H Me F H H H OMe 730. H Me Cl H F H H 731. H Me NO2 H Cl H H 732. H Me NO2 H H Me H 733. H Me F H H H I 734. H Me F H H H Br 735. H Me Br H H H Br 736. H Me Cl H H H Me 737. H Me Cl H H H OCHF2 738. H Me Cl H H H OMe 739. H Me Me H H H OMe 740. H Me OEt H H H CF3 741. H Me OC(O)Me H H H H 742. H Me OEt H H H Me 743. H Me Me Me H H Me 744. H Me Cl H H H C(O)OMe 745. H Me Cl H H OMe H 746. H Me F F H F F 747. H Me Cl H H F H 748. H Me F H H F Cl 749. H Me F H H Cl H 750. H Me Cl H H CF3 H 751. H Me Cl Me H H H 752. H Me OCHF2 H H H H 753. H Me OCH2CF3 H H H H 754. H Me CF3 H H H OCHF2 755. H Me CF3 H H H OCH2CF3 756. H Me Me H H H Me 757. H Me Cl H H H F 758. H Me F H F H H 759. H Me F Me H H Cl 760. H Me F H H OMe H 761. H Me Cl H OCH2O H 762. H Me Me H H F H 763. H Me OCF3 H H H H 764. H Me F F H H H 765. H Me OMe H H Cl H 766. NO2 H H H H H H 767. NO2 H F H H H H 768. NO2 H F H H F H 769. NO2 H F H H H F 770. NO2 H F Me H H F 771. NO2 H F H H H Cl 772. NO2 H CF3 H H H H 773. NO2 H Me H H H H 774. NO2 H F H H H CF3 775. NO2 H F CF3 H H F 776. NO2 H Br H H H H 777. NO2 H I H H H H 778. NO2 H Cl H H H H 779. NO2 H Cl H Cl H H 780. NO2 H Cl H H H Cl 781. NO2 H H Cl Cl H H 782. NO2 H Cl Cl Cl H H 783. NO2 H Cl Cl H Cl H 784. NO2 H Cl Cl Cl H Cl 785. NO2 H Cl Cl Cl Cl H 786. NO2 H Cl Cl Cl Cl Cl 787. NO2 H Cl Cl H H Cl 788. NO2 H Cl H Cl Cl H 789. NO2 H Cl H H Cl Cl 790. NO2 H H Cl Cl Cl H 791. NO2 H NO2 H H H H 792. NO2 H H Cl H H H 793. NO2 H H H Cl H H 794. NO2 H Cl H Cl H Cl 795. NO2 H Cl Cl H H H 796. NO2 H Cl H H Cl H 797. NO2 H H Cl H Cl H 798. NO2 H H OMe H H H 799. NO2 H C(O)OMe H H H H 800. NO2 H F Cl H H H 801. NO2 H F Me H H H 802. NO2 H H Me H H H 803. NO2 H OMe H H H H 804. NO2 H F F F H H 805. NO2 H F F H F H 806. NO2 H H F F F H 807. NO2 H F H F F H 808. NO2 H Me H Me H H 809. NO2 H Me H H Me H 810. NO2 H F H H CF3 H 811. NO2 H F H Br H H 812. NO2 H Me Me H H H 813. NO2 H F F F F F 814. NO2 H F H H H OMe 815. NO2 H Cl H F H H 816. NO2 H NO2 H Cl H H 817. NO2 H NO2 H H Me H 818. NO2 H F H H H I 819. NO2 H F H H H Br 820. NO2 H Br H H H Br 821. NO2 H Cl H H H Me 822. NO2 H Cl H H H OCHF2 823. NO2 H Cl H H H OMe 824. NO2 H Me H H H OMe 825. NO2 H OEt H H H CF3 826. NO2 H OC(O)Me H H H H 827. NO2 H OEt H H H Me 828. NO2 H Me Me H H Me 829. NO2 H Cl H H H C(O)OMe 830. NO2 H Cl H H OMe H 831. NO2 H F F H F F 832. NO2 H Cl H H F H 833. NO2 H F H H F Cl 834. NO2 H F H H Cl H 835. NO2 H Cl H H CF3 H 836. NO2 H Cl Me H H H 837. NO2 H OCHF2 H H H H 838. NO2 H OCH2CF3 H H H H 839. NO2 H CF3 H H H OCHF2 840. NO2 H CF3 H H H OCH2CF3 841. NO2 H Me H H H Me 842. NO2 H Cl H H H F 843. NO2 H F H F H H 844. NO2 H F Me H H Cl 845. NO2 H F H H OMe H 846. NO2 H Cl H OCH2O H 847. NO2 H Me H H F H 848. NO2 H OCF3 H H H H 849. NO2 H F F H H H 850. NO2 H OMe H H Cl H 851. CHF2 H H H H H H 852. CHF2 H F H H H H 853. CHF2 H F H H F H 854. CHF2 H F H H H F 855. CHF2 H F Me H H F 856. CHF2 H F H H H Cl 857. CHF2 H CF3 H H H H 858. CHF2 H Me H H H H 859. CHF2 H F H H H CF3 860. CHF2 H F CF3 H H F 861. CHF2 H Br H H H H 862. CHF2 H I H H H H 863. CHF2 H Cl H H H H 864. CHF2 H Cl H Cl H H 865. CHF2 H Cl H H H Cl 866. CHF2 H H Cl Cl H H 867. CHF2 H Cl Cl Cl H H 868. CHF2 H Cl Cl H Cl H 869. CHF2 H Cl Cl Cl H Cl 870. CHF2 H Cl Cl Cl Cl H 871. CHF2 H Cl Cl Cl Cl Cl 872. CHF2 H Cl Cl H H Cl 873. CHF2 H Cl H Cl Cl H 874. CHF2 H Cl H H Cl Cl 875. CHF2 H H Cl Cl Cl H 876. CHF2 H NO2 H H H H 877. CHF2 H H Cl H H H 878. CHF2 H H H Cl H H 879. CHF2 H Cl H Cl H Cl 880. CHF2 H Cl Cl H H H 881. CHF2 H Cl H H Cl H 882. CHF2 H H Cl H Cl H 883. CHF2 H H OMe H H H 884. CHF2 H C(O)OMe H H H H 885. CHF2 H F Cl H H H 886. CHF2 H F Me H H H 887. CHF2 H H Me H H H 888. CHF2 H OMe H H H H 889. CHF2 H F F F H H 890. CHF2 H F F H F H 891. CHF2 H H F F F H 892. CHF2 H F H F F H 893. CHF2 H Me H Me H H 894. CHF2 H Me H H Me H 895. CHF2 H F H H CF3 H 896. CHF2 H F H Br H H 897. CHF2 H Me Me H H H 898. CHF2 H F F F F F 899. CHF2 H F H H H OMe 900. CHF2 H Cl H F H H 901. CHF2 H NO2 H Cl H H 902. CHF2 H NO2 H H Me H 903. CHF2 H F H H H I 904. CHF2 H F H H H Br 905. CHF2 H Br H H H Br 906. CHF2 H Cl H H H Me 907. CHF2 H Cl H H H OCHF2 908. CHF2 H Cl H H H OMe 909. CHF2 H Me H H H OMe 910. CHF2 H OEt H H H CF3 911. CHF2 H OC(O)Me H H H H 912. CHF2 H OEt H H H Me 913. CHF2 H Me Me H H Me 914. CHF2 H Cl H H H C(O)OMe 915. CHF2 H Cl H H OMe H 916. CHF2 H F F H F F 917. CHF2 H Cl H H F H 918. CHF2 H F H H F Cl 919. CHF2 H F H H Cl H 920. CHF2 H Cl H H CF3 H 921. CHF2 H Cl Me H H H 922. CHF2 H OCHF2 H H H H 923. CHF2 H OCH2CF3 H H H H 924. CHF2 H CF3 H H H OCHF2 925. CHF2 H CF3 H H H OCH2CF3 926. CHF2 H Me H H H Me 927. CHF2 H Cl H H H F 928. CHF2 H F H F H H 929. CHF2 H F Me H H Cl 930. CHF2 H F H H OMe H 931. CHF2 H Cl H OCH2O H 932. CHF2 H Me H H F H 933. CHF2 H OCF3 H H H H 934. CHF2 H F F H H H 935. CHF2 H OMe H H Cl H 936. Cl Cl H H H H H 937. Cl Cl F H H H H 938. Cl Cl F H H F H 939. Cl Cl F H H H F 940. Cl Cl F Me H H F 941. Cl Cl F H H H Cl 942. Cl Cl CF3 H H H H 943. Cl Cl Me H H H H 944. Cl Cl F H H H CF3 945. Cl Cl F CF3 H H F 946. Cl Cl Br H H H H 947. Cl Cl I H H H H 948. Cl Cl Cl H H H H 949. Cl Cl Cl H Cl H H 950. Cl Cl Cl H H H Cl 951. Cl Cl H Cl Cl H H 952. Cl Cl Cl Cl Cl H H 953. Cl Cl Cl Cl H Cl H 954. Cl Cl Cl Cl Cl H Cl 955. Cl Cl Cl Cl Cl Cl H 956. Cl Cl Cl Cl Cl Cl Cl 957. Cl Cl Cl Cl H H Cl 958. Cl Cl Cl H Cl Cl H 959. Cl Cl Cl H H Cl Cl 960. Cl Cl H Cl Cl Cl H 961. Cl Cl NO2 H H H H 962. Cl Cl H Cl H H H 963. Cl Cl H H Cl H H 964. Cl Cl Cl H Cl H Cl 965. Cl Cl Cl Cl H H H 966. Cl Cl Cl H H Cl H 967. Cl Cl H Cl H Cl H 968. Cl Cl H OMe H H H 969. Cl Cl C(O)OMe H H H H 970. Cl Cl F Cl H H H 971. Cl Cl F Me H H H 972. Cl Cl H Me H H H 973. Cl Cl OMe H H H H 974. Cl Cl F F F H H 975. Cl Cl F F H F H 976. Cl Cl H F F F H 977. Cl Cl F H F F H 978. Cl Cl Me H Me H H 979. Cl Cl Me H H Me H 980. Cl Cl F H H CF3 H 981. Cl Cl F H Br H H 982. Cl Cl Me Me H H H 983. Cl Cl F F F F F 984. Cl Cl F H H H OMe 985. Cl Cl Cl H F H H 986. Cl Cl NO2 H Cl H H 987. Cl Cl NO2 H H Me H 988. Cl Cl F H H H I 989. Cl Cl F H H H Br 990. Cl Cl Br H H H Br 991. Cl Cl Cl H H H Me 992. Cl Cl Cl H H H OCHF2 993. Cl Cl Cl H H H OMe 994. Cl Cl Me H H H OMe 995. Cl Cl OEt H H H CF3 996. Cl Cl OC(O)Me H H H H 997. Cl Cl OEt H H H Me 998. Cl Cl Me Me H H Me 999. Cl Cl Cl H H H C(O)OMe 1000. Cl Cl Cl H H OMe H 1001. Cl Cl F F H F F 1002. Cl Cl Cl H H F H 1003. Cl Cl F H H F Cl 1004. Cl Cl F H H Cl H 1005. Cl Cl Cl H H CF3 H 1006. Cl Cl Cl Me H H H 1007. Cl Cl OCHF2 H H H H 1008. Cl Cl OCH2CF3 H H H H 1009. Cl Cl CF3 H H H OCHF2 1010. Cl Cl CF3 H H H OCH2CF3 1011. Cl Cl Me H H H Me 1012. Cl Cl Cl H H H F 1013. Cl Cl F H F H H 1014. Cl Cl F Me H H Cl 1015. Cl Cl F H H OMe H 1016. Cl Cl Cl H OCH2O H 1017. Cl Cl Me H H F H 1018. Cl Cl OCF3 H H H H 1019. Cl Cl F F H H H 1020. Cl Cl OMe H H Cl H 1021. Me Cl H H H H H 1022. Me Cl F H H H H 1023. Me Cl F H H F H 1024. Me Cl F H H H F 1025. Me Cl F Me H H F 1026. Me Cl F H H H Cl 1027. Me Cl CF3 H H H H 1028. Me Cl Me H H H H 1029. Me Cl F H H H CF3 1030. Me Cl F CF3 H H F 1031. Me Cl Br H H H H 1032. Me Cl I H H H H 1033. Me Cl Cl H H H H 1034. Me Cl Cl H Cl H H 1035. Me Cl Cl H H H Cl 1036. Me Cl H Cl Cl H H 1037. Me Cl Cl Cl Cl H H 1038. Me Cl Cl Cl H Cl H 1039. Me Cl Cl Cl Cl H Cl 1040. Me Cl Cl Cl Cl Cl H 1041. Me Cl Cl Cl Cl Cl Cl 1042. Me Cl Cl Cl H H Cl 1043. Me Cl Cl H Cl Cl H 1044. Me Cl Cl H H Cl Cl 1045. Me Cl H Cl Cl Cl H 1046. Me Cl NO2 H H H H 1047. Me Cl H Cl H H H 1048. Me Cl H H Cl H H 1049. Me Cl Cl H Cl H Cl 1050. Me Cl Cl Cl H H H 1051. Me Cl Cl H H Cl H 1052. Me Cl H Cl H Cl H 1053. Me Cl H OMe H H H 1054. Me Cl C(O)OMe H H H H 1055. Me Cl F Cl H H H 1056. Me Cl F Me H H H 1057. Me Cl H Me H H H 1058. Me Cl OMe H H H H 1059. Me Cl F F F H H 1060. Me Cl F F H F H 1061. Me Cl H F F F H 1062. Me Cl F H F F H 1063. Me Cl Me H Me H H 1064. Me Cl Me H H Me H 1065. Me Cl F H H CF3 H 1066. Me Cl F H Br H H 1067. Me Cl Me Me H H H 1068. Me Cl F F F F F 1069. Me Cl F H H H OMe 1070. Me Cl Cl H F H H 1071. Me Cl NO2 H Cl H H 1072. Me Cl NO2 H H Me H 1073. Me Cl F H H H I 1074. Me Cl F H H H Br 1075. Me Cl Br H H H Br 1076. Me Cl Cl H H H Me 1077. Me Cl Cl H H H OCHF2 1078. Me Cl Cl H H H OMe 1079. Me Cl Me H H H OMe 1080. Me Cl OEt H H H CF3 1081. Me Cl OC(O)Me H H H H 1082. Me Cl OEt H H H Me 1083. Me Cl Me Me H H Me 1084. Me Cl Cl H H H C(O)OMe 1085. Me Cl Cl H H OMe H 1086. Me Cl F F H F F 1087. Me Cl Cl H H F H 1088. Me Cl F H H F Cl 1089. Me Cl F H H Cl H 1090. Me Cl Cl H H CF3 H 1091. Me Cl Cl Me H H H 1092. Me Cl OCHF2 H H H H 1093. Me Cl OCH2CF3 H H H H 1094. Me Cl CF3 H H H OCHF2 1095. Me Cl CF3 H H H OCH2CF3 1096. Me Cl Me H H H Me 1097. Me Cl Cl H H H F 1098. Me Cl F H F H H 1099. Me Cl F Me H H Cl 1100. Me Cl F H H OMe H 1101. Me Cl Cl H OCH2O H 1102. Me Cl Me H H F H 1103. Me Cl OCF3 H H H H 1104. Me Cl F F H H H 1105. Me Cl OMe H H Cl H 1106. Cl Me H H H H H 1107. Cl Me F H H H H 1108. Cl Me F H H F H 1109. Cl Me F H H H F 1110. Cl Me F Me H H F 1111. Cl Me F H H H Cl 1112. Cl Me CF3 H H H H 1113. Cl Me Me H H H H 1114. Cl Me F H H H CF3 1115. Cl Me F CF3 H H F 1116. Cl Me Br H H H H 1117. Cl Me I H H H H 1118. Cl Me Cl H H H H 1119. Cl Me Cl H Cl H H 1120. Cl Me Cl H H H Cl 1121. Cl Me H Cl Cl H H 1122. Cl Me Cl Cl Cl H H 1123. Cl Me Cl Cl H Cl H 1124. Cl Me Cl Cl Cl H Cl 1125. Cl Me Cl Cl Cl Cl H 1126. Cl Me Cl Cl Cl Cl Cl 1127. Cl Me Cl Cl H H Cl 1128. Cl Me Cl H Cl Cl H 1129. Cl Me Cl H H Cl Cl 1130. Cl Me H Cl Cl Cl H 1131. Cl Me NO2 H H H H 1132. Cl Me H Cl H H H 1133. Cl Me H H Cl H H 1134. Cl Me Cl H Cl H Cl 1135. Cl Me Cl Cl H H H 1136. Cl Me Cl H H Cl H 1137. Cl Me H Cl H Cl H 1138. Cl Me H OMe H H H 1139. Cl Me C(O)OMe H H H H 1140. Cl Me F Cl H H H 1141. Cl Me F Me H H H 1142. Cl Me H Me H H H 1143. Cl Me OMe H H H H 1144. Cl Me F F F H H 1145. Cl Me F F H F H 1146. Cl Me H F F F H 1147. Cl Me F H F F H 1148. Cl Me Me H Me H H 1149. Cl Me Me H H Me H 1150. Cl Me F H H CF3 H 1151. Cl Me F H Br H H 1152. Cl Me Me Me H H H 1153. Cl Me F F F F F 1154. Cl Me F H H H OMe 1155. Cl Me Cl H F H H 1156. Cl Me NO2 H Cl H H 1157. Cl Me NO2 H H Me H 1158. Cl Me F H H H I 1159. Cl Me F H H H Br 1160. Cl Me Br H H H Br 1161. Cl Me Cl H H H Me 1162. Cl Me Cl H H H OCHF2 1163. Cl Me Cl H H H OMe 1164. Cl Me Me H H H OMe 1165. Cl Me OEt H H H CF3 1166. Cl Me OC(O)Me H H H H 1167. Cl Me OEt H H H Me 1168. Cl Me Me Me H H Me 1169. Cl Me Cl H H H C(O)OMe 1170. Cl Me Cl H H OMe H 1171. Cl Me F F H F F 1172. Cl Me Cl H H F H 1173. Cl Me F H H F Cl 1174. Cl Me F H H Cl H 1175. Cl Me Cl H H CF3 H 1176. Cl Me Cl Me H H H 1177. Cl Me OCHF2 H H H H 1178. Cl Me OCH2CF3 H H H H 1179. Cl Me CF3 H H H OCHF2 1180. Cl Me CF3 H H H OCH2CF3 1181. Cl Me Me H H H Me 1182. Cl Me Cl H H H F 1183. Cl Me F H F H H 1184. Cl Me F Me H H Cl 1185. Cl Me F H H OMe H 1186. Cl Me Cl H OCH2O H 1187. Cl Me Me H H F H 1188. Cl Me OCF3 H H H H 1189. Cl Me F F H H H 1190. Cl Me OMe H H Cl H

TABLE 2 Compounds of the formula Ia-R ( Ia-R ) Ex. No. R11 R12 R1 R2 R3 R4 R5 1191. H H H H H H H 1192. H H F H H H H 1193. H H F H H F H 1194. H H F H H H F 1195. H H F Me H H F 1196. H H F H H H Cl 1197. H H CF3 H H H H 1198. H H Me H H H H 1199. H H F H H H CF3 1200. H H F CF3 H H F 1201. H H Br H H H H 1202. H H I H H H H 1203. H H Cl H H H H 1204. H H Cl H Cl H H 1205. H H Cl H H H Cl 1206. H H H Cl Cl H H 1207. H H Cl Cl Cl H H 1208. H H Cl Cl H Cl H 1209. H H Cl Cl Cl H Cl 1210. H H Cl Cl Cl Cl H 1211. H H Cl Cl Cl Cl Cl 1212. H H Cl Cl H H Cl 1213. H H Cl H Cl Cl H 1214. H H Cl H H Cl Cl 1215. H H H Cl Cl Cl H 1216. H H NO2 H H H H 1217. H H H Cl H H H 1218. H H H H Cl H H 1219. H H Cl H Cl H Cl 1220. H H Cl Cl H H H 1221. H H Cl H H Cl H 1222. H H H Cl H Cl H 1223. H H H OMe H H H 1224. H H C(O)OMe H H H H 1225. H H F Cl H H H 1226. H H F Me H H H 1227. H H H Me H H H 1228. H H OMe H H H H 1229. H H F F F H H 1230. H H F F H F H 1231. H H H F F F H 1232. H H F H F F H 1233. H H Me H Me H H 1234. H H Me H H Me H 1235. H H F H H CF3 H 1236. H H F H Br H H 1237. H H Me Me H H H 1238. H H F F F F F 1239. H H F H H H OMe 1240. H H Cl H F H H 1241. H H NO2 H Cl H H 1242. H H NO2 H H Me H 1243. H H F H H H I 1244. H H F H H H Br 1245. H H Br H H H Br 1246. H H Cl H H H Me 1247. H H Cl H H H OCHF2 1248. H H Cl H H H OMe 1249. H H Me H H H OMe 1250. H H OEt H H H CF3 1251. H H OC(O)Me H H H H 1252. H H OEt H H H Me 1253. H H Me Me H H Me 1254. H H Cl H H H C(O)OMe 1255. H H Cl H H OMe H 1256. H H F F H F F 1257. H H Cl H H F H 1258. H H F H H F Cl 1259. H H F H H Cl H 1260. H H Cl H H CF3 H 1261. H H Cl Me H H H 1262. H H OCHF2 H H H H 1263. H H OCH2CF3 H H H H 1264. H H CF3 H H H OCHF2 1265. H H CF3 H H H OCH2CF3 1266. H H Me H H H Me 1267. H H Cl H H H F 1268. H H F H F H H 1269. H H F Me H H Cl 1270. H H F H H OMe H 1271. H H Cl H OCH2O H 1272. H H Me H H F H 1273. H H OCF3 H H H H 1274. H H F F H H H 1275. H H OMe H H Cl H 1276. F H H H H H H 1277. F H F H H H H 1278. F H F H H F H 1279. F H F H H H F 1280. F H F Me H H F 1281. F H F H H H Cl 1282. F H CF3 H H H H 1283. F H Me H H H H 1284. F H F H H H CF3 1285. F H F CF3 H H F 1286. F H Br H H H H 1287. F H I H H H H 1288. F H Cl H H H H 1289. F H Cl H Cl H H 1290. F H Cl H H H Cl 1291. F H H Cl Cl H H 1292. F H Cl Cl Cl H H 1293. F H Cl Cl H Cl H 1294. F H Cl Cl Cl H Cl 1295. F H Cl Cl Cl Cl H 1296. F H Cl Cl Cl Cl Cl 1297. F H Cl Cl H H Cl 1298. F H Cl H Cl Cl H 1299. F H Cl H H Cl Cl 1300. F H H Cl Cl Cl H 1301. F H NO2 H H H H 1302. F H H Cl H H H 1303. F H H H Cl H H 1304. F H Cl H Cl H Cl 1305. F H Cl Cl H H H 1306. F H Cl H H Cl H 1307. F H H Cl H Cl H 1308. F H H OMe H H H 1309. F H C(O)OMe H H H H 1310. F H F Cl H H H 1311. F H F Me H H H 1312. F H H Me H H H 1313. F H OMe H H H H 1314. F H F F F H H 1315. F H F F H F H 1316. F H H F F F H 1317. F H F H F F H 1318. F H Me H Me H H 1319. F H Me H H Me H 1320. F H F H H CF3 H 1321. F H F H Br H H 1322. F H Me Me H H H 1323. F H F F F F F 1324. F H F H H H OMe 1325. F H Cl H F H H 1326. F H NO2 H Cl H H 1327. F H NO2 H H Me H 1328. F H F H H H I 1329. F H F H H H Br 1330. F H Br H H H Br 1331. F H Cl H H H Me 1332. F H Cl H H H OCHF2 1333. F H Cl H H H OMe 1334. F H Me H H H OMe 1335. F H OEt H H H CF3 1336. F H OC(O)Me H H H H 1337. F H OEt H H H Me 1338. F H Me Me H H Me 1339. F H Cl H H H C(O)OMe 1340. F H Cl H H OMe H 1341. F H F F H F F 1342. F H Cl H H F H 1343. F H F H H F Cl 1344. F H F H H Cl H 1345. F H Cl H H CF3 H 1346. F H Cl Me H H H 1347. F H OCHF2 H H H H 1348. F H OCH2CF3 H H H H 1349. F H CF3 H H H OCHF2 1350. F H CF3 H H H OCH2CF3 1351. F H Me H H H Me 1352. F H Cl H H H F 1353. F H F H F H H 1354. F H F Me H H Cl 1355. F H F H H OMe H 1356. F H Cl H OCH2O H 1357. F H Me H H F H 1358. F H OCF3 H H H H 1359. F H F F H H H 1360. F H OMe H H Cl H 1361. Cl H H H H H H 1362. Cl H F H H H H 1363. Cl H F H H F H 1364. Cl H F H H H F 1365. Cl H F Me H H F 1366. Cl H F H H H Cl 1367. Cl H CF3 H H H H 1368. Cl H Me H H H H 1369. Cl H F H H H CF3 1370. Cl H F CF3 H H F 1371. Cl H Br H H H H 1372. Cl H I H H H H 1373. Cl H Cl H H H H 1374. Cl H Cl H Cl H H 1375. Cl H Cl H H H Cl 1376. Cl H H Cl Cl H H 1377. Cl H Cl Cl Cl H H 1378. Cl H Cl Cl H Cl H 1379. Cl H Cl Cl Cl H Cl 1380. Cl H Cl Cl Cl Cl H 1381. Cl H Cl Cl Cl Cl Cl 1382. Cl H Cl Cl H H Cl 1383. Cl H Cl H Cl Cl H 1384. Cl H Cl H H Cl Cl 1385. Cl H H Cl Cl Cl H 1386. Cl H NO2 H H H H 1387. Cl H H Cl H H H 1388. Cl H H H Cl H H 1389. Cl H Cl H Cl H Cl 1390. Cl H Cl Cl H H H 1391. Cl H Cl H H Cl H 1392. Cl H H Cl H Cl H 1393. Cl H H OMe H H H 1394. Cl H C(O)OMe H H H H 1395. Cl H F Cl H H H 1396. Cl H F Me H H H 1397. Cl H H Me H H H 1398. Cl H OMe H H H H 1399. Cl H F F F H H 1400. Cl H F F H F H 1401. Cl H H F F F H 1402. Cl H F H F F H 1403. Cl H Me H Me H H 1404. Cl H Me H H Me H 1405. Cl H F H H CF3 H 1406. Cl H F H Br H H 1407. Cl H Me Me H H H 1408. Cl H F F F F F 1409. Cl H F H H H OMe 1410. Cl H Cl H F H H 1411. Cl H NO2 H Cl H H 1412. Cl H NO2 H H Me H 1413. Cl H F H H H I 1414. Cl H F H H H Br 1415. Cl H Br H H H Br 1416. Cl H Cl H H H Me 1417. Cl H Cl H H H OCHF2 1418. Cl H Cl H H H OMe 1419. Cl H Me H H H OMe 1420. Cl H OEt H H H CF3 1421. Cl H OC(O)Me H H H H 1422. Cl H OEt H H H Me 1423. Cl H Me Me H H Me 1424. Cl H Cl H H H C(O)OMe 1425. Cl H Cl H H OMe H 1426. Cl H F F H F F 1427. Cl H Cl H H F H 1428. Cl H F H H F Cl 1429. Cl H F H H Cl H 1430. Cl H Cl H H CF3 H 1431. Cl H Cl Me H H H 1432. Cl H OCHF2 H H H H 1433. Cl H OCH2CF3 H H H H 1434. Cl H CF3 H H H OCHF2 1435. Cl H CF3 H H H OCH2CF3 1436. Cl H Me H H H Me 1437. Cl H Cl H H H F 1438. Cl H F H F H H 1439. Cl H F Me H H Cl 1440. Cl H F H H OMe H 1441. Cl H Cl H OCH2O H 1442. Cl H Me H H F H 1443. Cl H OCF3 H H H H 1444. Cl H F F H H H 1445. Cl H OMe H H Cl H 1446. Br H H H H H H 1447. Br H F H H H H 1448. Br H F H H F H 1449. Br H F H H H F 1450. Br H F Me H H F 1451. Br H F H H H Cl 1452. Br H CF3 H H H H 1453. Br H Me H H H H 1454. Br H F H H H CF3 1455. Br H F CF3 H H F 1456. Br H Br H H H H 1457. Br H I H H H H 1458. Br H Cl H H H H 1459. Br H Cl H Cl H H 1460. Br H Cl H H H Cl 1461. Br H H Cl Cl H H 1462. Br H Cl Cl Cl H H 1463. Br H Cl Cl H Cl H 1464. Br H Cl Cl Cl H Cl 1465. Br H Cl Cl Cl Cl H 1466. Br H Cl Cl Cl Cl Cl 1467. Br H Cl Cl H H Cl 1468. Br H Cl H Cl Cl H 1469. Br H Cl H H Cl Cl 1470. Br H H Cl Cl Cl H 1471. Br H NO2 H H H H 1472. Br H H Cl H H H 1473. Br H H H Cl H H 1474. Br H Cl H Cl H Cl 1475. Br H Cl Cl H H H 1476. Br H Cl H H Cl H 1477. Br H H Cl H Cl H 1478. Br H H OMe H H H 1479. Br H C(O)OMe H H H H 1480. Br H F Cl H H H 1481. Br H F Me H H H 1482. Br H H Me H H H 1483. Br H OMe H H H H 1484. Br H F F F H H 1485. Br H F F H F H 1486. Br H H F F F H 1487. Br H F H F F H 1488. Br H Me H Me H H 1489. Br H Me H H Me H 1490. Br H F H H CF3 H 1491. Br H F H Br H H 1492. Br H Me Me H H H 1493. Br H F F F F F 1494. Br H F H H H OMe 1495. Br H Cl H F H H 1496. Br H NO2 H Cl H H 1497. Br H NO2 H H Me H 1498. Br H F H H H I 1499. Br H F H H H Br 1500. Br H Br H H H Br 1501. Br H Cl H H H Me 1502. Br H Cl H H H OCHF2 1503. Br H Cl H H H OMe 1504. Br H Me H H H OMe 1505. Br H OEt H H H CF3 1506. Br H OC(O)Me H H H H 1507. Br H OEt H H H Me 1508. Br H Me Me H H Me 1509. Br H Cl H H H C(O)OMe 1510. Br H Cl H H OMe H 1511. Br H F F H F F 1512. Br H Cl H H F H 1513. Br H F H H F Cl 1514. Br H F H H Cl H 1515. Br H Cl H H CF3 H 1516. Br H Cl Me H H H 1517. Br H OCHF2 H H H H 1518. Br H OCH2CF3 H H H H 1519. Br H CF3 H H H OCHF2 1520. Br H CF3 H H H OCH2CF3 1521. Br H Me H H H Me 1522. Br H Cl H H H F 1523. Br H F H F H H 1524. Br H F Me H H Cl 1525. Br H F H H OMe H 1526. Br H Cl H OCH2O H 1527. Br H Me H H F H 1528. Br H OCF3 H H H H 1529. Br H F F H H H 1530. Br H OMe H H Cl H 1531. I H H H H H H 1532. I H F H H H H 1533. I H F H H F H 1534. I H F H H H F 1535. I H F Me H H F 1536. I H F H H H Cl 1537. I H CF3 H H H H 1538. I H Me H H H H 1539. I H F H H H CF3 1540. I H F CF3 H H F 1541. I H Br H H H H 1542. I H I H H H H 1543. I H Cl H H H H 1544. I H Cl H Cl H H 1545. I H Cl H H H Cl 1546. I H H Cl Cl H H 1547. I H Cl Cl Cl H H 1548. I H Cl Cl H Cl H 1549. I H Cl Cl Cl H Cl 1550. I H Cl Cl Cl Cl H 1551. I H Cl Cl Cl Cl Cl 1552. I H Cl Cl H H Cl 1553. I H Cl H Cl Cl H 1554. I H Cl H H Cl Cl 1555. I H H Cl Cl Cl H 1556. I H NO2 H H H H 1557. I H H Cl H H H 1558. I H H H Cl H H 1559. I H Cl H Cl H Cl 1560. I H Cl Cl H H H 1561. I H Cl H H Cl H 1562. I H H Cl H Cl H 1563. I H H OMe H H H 1564. I H C(O)OMe H H H H 1565. I H F Cl H H H 1566. I H F Me H H H 1567. I H H Me H H H 1568. I H OMe H H H H 1569. I H F F F H H 1570. I H F F H F H 1571. I H H F F F H 1572. I H F H F F H 1573. I H Me H Me H H 1574. I H Me H H Me H 1575. I H F H H CF3 H 1576. I H F H Br H H 1577. I H Me Me H H H 1578. I H F F F F F 1579. I H F H H H OMe 1580. I H Cl H F H H 1581. I H NO2 H Cl H H 1582. I H NO2 H H Me H 1583. I H F H H H I 1584. I H F H H H Br 1585. I H Br H H H Br 1586. I H Cl H H H Me 1587. I H Cl H H H OCHF2 1588. I H Cl H H H OMe 1589. I H Me H H H OMe 1590. I H OEt H H H CF3 1591. I H OC(O)Me H H H H 1592. I H OEt H H H Me 1593. I H Me Me H H Me 1594. I H Cl H H H C(O)OMe 1595. I H Cl H H OMe H 1596. I H F F H F F 1597. I H Cl H H F H 1598. I H F H H F Cl 1599. I H F H H Cl H 1600. I H Cl H H CF3 H 1601. I H Cl Me H H H 1602. I H OCHF2 H H H H 1603. I H OCH2CF3 H H H H 1604. I H CF3 H H H OCHF2 1605. I H CF3 H H H OCH2CF3 1606. I H Me H H H Me 1607. I H Cl H H H F 1608. I H F H F H H 1609. I H F Me H H Cl 1610. I H F H H OMe H 1611. I H Cl H OCH2O H 1612. I H Me H H F H 1613. I H OCF3 H H H H 1614. I H F F H H H 1615. I H OMe H H Cl H 1616. H Cl H H H H H 1617. H Cl F H H H H 1618. H Cl F H H F H 1619. H Cl F H H H F 1620. H Cl F Me H H F 1621. H Cl F H H H Cl 1622. H Cl CF3 H H H H 1623. H Cl Me H H H H 1624. H Cl F H H H CF3 1625. H Cl F CF3 H H F 1626. H Cl Br H H H H 1627. H Cl I H H H H 1628. H Cl Cl H H H H 1629. H Cl Cl H Cl H H 1630. H Cl Cl H H H Cl 1631. H Cl H Cl Cl H H 1632. H Cl Cl Cl Cl H H 1633. H Cl Cl Cl H Cl H 1634. H Cl Cl Cl Cl H Cl 1635. H Cl Cl Cl Cl Cl H 1636. H Cl Cl Cl Cl Cl Cl 1637. H Cl Cl Cl H H Cl 1638. H Cl Cl H Cl Cl H 1639. H Cl Cl H H Cl Cl 1640. H Cl H Cl Cl Cl H 1641. H Cl NO2 H H H H 1642. H Cl H Cl H H H 1643. H Cl H H Cl H H 1644. H Cl Cl H Cl H Cl 1645. H Cl Cl Cl H H H 1646. H Cl Cl H H Cl H 1647. H Cl H Cl H Cl H 1648. H Cl H OMe H H H 1649. H Cl C(O)OMe H H H H 1650. H Cl F Cl H H H 1651. H Cl F Me H H H 1652. H Cl H Me H H H 1653. H Cl OMe H H H H 1654. H Cl F F F H H 1655. H Cl F F H F H 1656. H Cl H F F F H 1657. H Cl F H F F H 1658. H Cl Me H Me H H 1659. H Cl Me H H Me H 1660. H Cl F H H CF3 H 1661. H Cl F H Br H H 1662. H Cl Me Me H H H 1663. H Cl F F F F F 1664. H Cl F H H H OMe 1665. H Cl Cl H F H H 1666. H Cl NO2 H Cl H H 1667. H Cl NO2 H H Me H 1668. H Cl F H H H I 1669. H Cl F H H H Br 1670. H Cl Br H H H Br 1671. H Cl Cl H H H Me 1672. H Cl Cl H H H OCHF2 1673. H Cl Cl H H H OMe 1674. H Cl Me H H H OMe 1675. H Cl OEt H H H CF3 1676. H Cl OC(O)Me H H H H 1677. H Cl OEt H H H Me 1678. H Cl Me Me H H Me 1679. H Cl Cl H H H C(O)OMe 1680. H Cl Cl H H OMe H 1681. H Cl F F H F F 1682. H Cl Cl H H F H 1683. H Cl F H H F Cl 1684. H Cl F H H Cl H 1685. H Cl Cl H H CF3 H 1686. H Cl Cl Me H H H 1687. H Cl OCHF2 H H H H 1688. H Cl OCH2CF3 H H H H 1689. H Cl CF3 H H H OCHF2 1690. H Cl CF3 H H H OCH2CF3 1691. H Cl Me H H H Me 1692. H Cl Cl H H H F 1693. H Cl F H F H H 1694. H Cl F Me H H Cl 1695. H Cl F H H OMe H 1696. H Cl Cl H OCH2O H 1697. H Cl Me H H F H 1698. H Cl OCF3 H H H H 1699. H Cl F F H H H 1700. H Cl OMe H H Cl H 1701. H Br H H H H H 1702. H Br F H H H H 1703. H Br F H H F H 1704. H Br F H H H F 1705. H Br F Me H H F 1706. H Br F H H H Cl 1707. H Br CF3 H H H H 1708. H Br Me H H H H 1709. H Br F H H H CF3 1710. H Br F CF3 H H F 1711. H Br Br H H H H 1712. H Br I H H H H 1713. H Br Cl H H H H 1714. H Br Cl H Cl H H 1715. H Br Cl H H H Cl 1716. H Br H Cl Cl H H 1717. H Br Cl Cl Cl H H 1718. H Br Cl Cl H Cl H 1719. H Br Cl Cl Cl H Cl 1720. H Br Cl Cl Cl Cl H 1721. H Br Cl Cl Cl Cl Cl 1722. H Br Cl Cl H H Cl 1723. H Br Cl H Cl Cl H 1724. H Br Cl H H Cl Cl 1725. H Br H Cl Cl Cl H 1726. H Br NO2 H H H H 1727. H Br H Cl H H H 1728. H Br H H Cl H H 1729. H Br Cl H Cl H Cl 1730. H Br Cl Cl H H H 1731. H Br Cl H H Cl H 1732. H Br H Cl H Cl H 1733. H Br H OMe H H H 1734. H Br C(O)OMe H H H H 1735. H Br F Cl H H H 1736. H Br F Me H H H 1737. H Br H Me H H H 1738. H Br OMe H H H H 1739. H Br F F F H H 1740. H Br F F H F H 1741. H Br H F F F H 1742. H Br F H F F H 1743. H Br Me H Me H H 1744. H Br Me H H Me H 1745. H Br F H H CF3 H 1746. H Br F H Br H H 1747. H Br Me Me H H H 1748. H Br F F F F F 1749. H Br F H H H OMe 1750. H Br Cl H F H H 1751. H Br NO2 H Cl H H 1752. H Br NO2 H H Me H 1753. H Br F H H I I 1754. H Br F H H H Br 1755. H Br Br H H H Br 1756. H Br Cl H H H Me 1757. H Br Cl H H H OCHF2 1758. H Br Cl H H H OMe 1759. H Br Me H H H OMe 1760. H Br OEt H H H CF3 1761. H Br OC(O)Me H H H H 1762. H Br OEt H H H Me 1763. H Br Me Me H H Me 1764. H Br Cl H H H C(O)OMe 1765. H Br Cl H H OMe H 1766. H Br F F H F F 1767. H Br Cl H H F H 1768. H Br F H H F Cl 1769. H Br F H H Cl H 1770. H Br Cl H H CF3 H 1771. H Br Cl Me H H H 1772. H Br OCHF2 H H H H 1773. H Br OCH2CF3 H H H H 1774. H Br CF3 H H H OCHF2 1775. H Br CF3 H H H OCH2CF3 1776. H Br Me H H H Me 1777. H Br Cl H H H F 1778. H Br F H F H H 1779. H Br F Me H H Cl 1780. H Br F H H OMe H 1781. H Br Cl H OCH2O H 1782. H Br Me H H F H 1783. H Br OCF3 H H H H 1784. H Br F F H H H 1785. H Br OMe H H Cl H 1786. Me H H H H H H 1787. Me H F H H H H 1788. Me H F H H F H 1789. Me H F H H H F 1790. Me H F Me H H F 1791. Me H F H H H Cl 1792. Me H CF3 H H H H 1793. Me H Me H H H H 1794. Me H F H H H CF3 1795. Me H F CF3 H H F 1796. Me H Br H H H H 1797. Me H I H H H H 1798. Me H Cl H H H H 1799. Me H Cl H Cl H H 1800. Me H Cl H H H Cl 1801. Me H H Cl Cl H H 1802. Me H Cl Cl Cl H H 1803. Me H Cl Cl H Cl H 1804. Me H Cl Cl Cl H Cl 1805. Me H Cl Cl Cl Cl H 1806. Me H Cl Cl Cl Cl Cl 1807. Me H Cl Cl H H Cl 1808. Me H Cl H Cl Cl H 1809. Me H Cl H H Cl Cl 1810. Me H H Cl Cl Cl H 1811. Me H NO2 H H H H 1812. Me H H Cl H H H 1813. Me H H H Cl H H 1814. Me H Cl H Cl H Cl 1815. Me H Cl Cl H H H 1816. Me H Cl H H Cl H 1817. Me H H Cl H Cl H 1818. Me H H OMe H H H 1819. Me H C(O)OMe H H H H 1820. Me H F Cl H H H 1821. Me H F Me H H H 1822. Me H H Me H H H 1823. Me H OMe H H H H 1824. Me H F F F H H 1825. Me H F F H F H 1826. Me H H F F F H 1827. Me H F H F F H 1828. Me H Me H Me H H 1829. Me H Me H H Me H 1830. Me H F H H CF3 H 1831. Me H F H Br H H 1832. Me H Me Me H H H 1833. Me H F F F F F 1834. Me H F H H H OMe 1835. Me H Cl H F H H 1836. Me H NO2 H Cl H H 1837. Me H NO2 H H Me H 1838. Me H F H H H I 1839. Me H F H H H Br 1840. Me H Br H H H Br 1841. Me H Cl H H H Me 1842. Me H Cl H H H OCHF2 1843. Me H Cl H H H OMe 1844. Me H Me H H H OMe 1845. Me H OEt H H H CF3 1846. Me H OC(O)Me H H H H 1847. Me H OEt H H H Me 1848. Me H Me Me H H Me 1849. Me H Cl H H H C(O)OMe 1850. Me H Cl H H OMe H 1851. Me H F F H F F 1852. Me H Cl H H F H 1853. Me H F H H F Cl 1854. Me H F H H Cl H 1855. Me H Cl H H CF3 H 1856. Me H Cl Me H H H 1857. Me H OCHF2 H H H H 1858. Me H OCH2CF3 H H H H 1859. Me H CF3 H H H OCHF2 1860. Me H CF3 H H H OCH2CF3 1861. Me H Me H H H Me 1862. Me H Cl H H H F 1863. Me H F H F H H 1864. Me H F Me H H Cl 1865. Me H F H H OMe H 1866. Me H Cl H OCH2O H 1867. Me H Me H H F H 1868. Me H OCF3 H H H H 1869. Me H F F H H H 1870. Me H OMe H H Cl H 1871. H Me H H H H H 1872. H Me F H H H H 1873. H Me F H H F H 1874. H Me F H H H F 1875. H Me F Me H H F 1876. H Me F H H H Cl 1877. H Me CF3 H H H H 1878. H Me Me H H H H 1879. H Me F H H H CF3 1880. H Me F CF3 H H F 1881. H Me Br H H H H 1882. H Me I H H H H 1883. H Me Cl H H H H 1884. H Me Cl H Cl H H 1885. H Me Cl H H H Cl 1886. H Me H Cl Cl H H 1887. H Me Cl Cl Cl H H 1888. H Me Cl Cl H Cl H 1889. H Me Cl Cl Cl H Cl 1890. H Me Cl Cl Cl Cl H 1891. H Me Cl Cl Cl Cl Cl 1892. H Me Cl Cl H H Cl 1893. H Me Cl H Cl Cl H 1894. H Me Cl H H Cl Cl 1895. H Me H Cl Cl Cl H 1896. H Me NO2 H H H H 1897. H Me H Cl H H H 1898. H Me H H Cl H H 1899. H Me Cl H Cl H Cl 1900. H Me Cl Cl H H H 1901. H Me Cl H H Cl H 1902. H Me H Cl H Cl H 1903. H Me H OMe H H H 1904. H Me C(O)OMe H H H H 1905. H Me F Cl H H H 1906. H Me F Me H H H 1907. H Me H Me H H H 1908. H Me OMe H H H H 1909. H Me F F F H H 1910. H Me F F H F H 1911. H Me H F F F H 1912. H Me F H F F H 1913. H Me Me H Me H H 1914. H Me Me H H Me H 1915. H Me F H H CF3 H 1916. H Me F H Br H H 1917. H Me Me Me H H H 1918. H Me F F F F F 1919. H Me F H H H OMe 1920. H Me Cl H F H H 1921. H Me NO2 H Cl H H 1922. H Me NO2 H H Me H 1923. H Me F H H H I 1924. H Me F H H H Br 1925. H Me Br H H H Br 1926. H Me Cl H H H Me 1927. H Me Cl H H H OCHF2 1928. H Me Cl H H H OMe 1929. H Me Me H H H OMe 1930. H Me OEt H H H CF3 1931. H Me OC(O)Me H H H H 1932. H Me OEt H H H Me 1933. H Me Me Me H H Me 1934. H Me Cl H H H C(O)OMe 1935. H Me Cl H H OMe H 1936. H Me F F H F F 1937. H Me Cl H H F H 1938. H Me F H H F Cl 1939. H Me F H H Cl H 1940. H Me Cl H H CF3 H 1941. H Me Cl Me H H H 1942. H Me OCHF2 H H H H 1943. H Me OCH2CF3 H H H H 1944. H Me CF3 H H H OCHF2 1945. H Me CF3 H H H OCH2CF3 1946. H Me Me H H H Me 1947. H Me Cl H H H F 1948. H Me F H F H H 1949. H Me F Me H H Cl 1950. H Me F H H OMe H 1951. H Me Cl H OCH2O H 1952. H Me Me H H F H 1953. H Me OCF3 H H H H 1954. H Me F F H H H 1955. H Me OMe H H Cl H 1956. NO2 H H H H H H 1957. NO2 H F H H H H 1958. NO2 H F H H F H 1959. NO2 H F H H H F 1960. NO2 H F Me H H F 1961. NO2 H F H H H Cl 1962. NO2 H CF3 H H H H 1963. NO2 H Me H H H H 1964. NO2 H F H H H CF3 1965. NO2 H F CF3 H H F 1966. NO2 H Br H H H H 1967. NO2 H I H H H H 1968. NO2 H Cl H H H H 1969. NO2 H Cl H Cl H H 1970. NO2 H Cl H H H Cl 1971. NO2 H H Cl Cl H H 1972. NO2 H Cl Cl Cl H H 1973. NO2 H Cl Cl H Cl H 1974. NO2 H Cl Cl Cl H Cl 1975. NO2 H Cl Cl Cl Cl H 1976. NO2 H Cl Cl Cl Cl Cl 1977. NO2 H Cl Cl H H Cl 1978. NO2 H Cl H Cl Cl H 1979. NO2 H Cl H H Cl Cl 1980. NO2 H H Cl Cl Cl H 1981. NO2 H NO2 H H H H 1982. NO2 H H Cl H H H 1983. NO2 H H H Cl H H 1984. NO2 H Cl H Cl H Cl 1985. NO2 H Cl Cl H H H 1986. NO2 H Cl H H Cl H 1987. NO2 H H Cl H Cl H 1988. NO2 H H OMe H H H 1989. NO2 H C(O)OMe H H H H 1990. NO2 H F Cl H H H 1991. NO2 H F Me H H H 1992. NO2 H H Me H H H 1993. NO2 H OMe H H H H 1994. NO2 H F F F H H 1995. NO2 H F F H F H 1996. NO2 H H F F F H 1997. NO2 H F H F F H 1998. NO2 H Me H Me H H 1999. NO2 H Me H H Me H 2000. NO2 H F H H CF3 H 2001. NO2 H F H Br H H 2002. NO2 H Me Me H H H 2003. NO2 H F F F F F 2004. NO2 H F H H H OMe 2005. NO2 H Cl H F H H 2006. NO2 H NO2 H Cl H H 2007. NO2 H NO2 H H Me H 2008. NO2 H F H H H I 2009. NO2 H F H H H Br 2010. NO2 H Br H H H Br 2011. NO2 H Cl H H H Me 2012. NO2 H Cl H H H OCHF2 2013. NO2 H Cl H H H OMe 2014. NO2 H Me H H H OMe 2015. NO2 H OEt H H H CF3 2016. NO2 H OC(O)Me H H H H 2017. NO2 H OEt H H H Me 2018. NO2 H Me Me H H Me 2019. NO2 H Cl H H H C(O)OMe 2020. NO2 H Cl H H OMe H 2021. NO2 H F F H F F 2022. NO2 H Cl H H F H 2023. NO2 H F H H F Cl 2024. NO2 H F H H Cl H 2025. NO2 H Cl H H CF3 H 2026. NO2 H Cl Me H H H 2027. NO2 H OCHF2 H H H H 2028. NO2 H OCH2CF3 H H H H 2029. NO2 H CF3 H H H OCHF2 2030. NO2 H CF3 H H H OCH2CF3 2031. NO2 H Me H H H Me 2032. NO2 H Cl H H H F 2033. NO2 H F H F H H 2034. NO2 H F Me H H Cl 2035. NO2 H F H H OMe H 2036. NO2 H Cl H OCH2O H 2037. NO2 H Me H H F H 2038. NO2 H OCF3 H H H H 2039. NO2 H F F H H H 2040. NO2 H OMe H H Cl H 2041. CHF2 H H H H H H 2042. CHF2 H F H H H H 2043. CHF2 H F H H F H 2044. CHF2 H F H H H F 2045. CHF2 H F Me H H F 2046. CHF2 H F H H H Cl 2047. CHF2 H CF3 H H H H 2048. CHF2 H Me H H H H 2049. CHF2 H F H H H CF3 2050. CHF2 H F CF3 H H F 2051. CHF2 H Br H H H H 2052. CHF2 H I H H H H 2053. CHF2 H Cl H H H H 2054. CHF2 H Cl H Cl H H 2055. CHF2 H Cl H H H Cl 2056. CHF2 H H Cl Cl H H 2057. CHF2 H Cl Cl Cl H H 2058. CHF2 H Cl Cl H Cl H 2059. CHF2 H Cl Cl Cl H Cl 2060. CHF2 H Cl Cl Cl Cl H 2061. CHF2 H Cl Cl Cl Cl Cl 2062. CHF2 H Cl Cl H H Cl 2063. CHF2 H Cl H Cl Cl H 2064. CHF2 H Cl H H Cl Cl 2065. CHF2 H H Cl Cl Cl H 2066. CHF2 H NO2 H H H H 2067. CHF2 H H Cl H H H 2068. CHF2 H H H Cl H H 2069. CHF2 H Cl H Cl H Cl 2070. CHF2 H Cl Cl H H H 2071. CHF2 H Cl H H Cl H 2072. CHF2 H H Cl H Cl H 2073. CHF2 H H OMe H H H 2074. CHF2 H C(O)OMe H H H H 2075. CHF2 H F Cl H H H 2076. CHF2 H F Me H H H 2077. CHF2 H H Me H H H 2078. CHF2 H OMe H H H H 2079. CHF2 H F F F H H 2080. CHF2 H F F H F H 2081. CHF2 H H F F F H 2082. CHF2 H F H F F H 2083. CHF2 H Me H Me H H 2084. CHF2 H Me H H Me H 2085. CHF2 H F H H CF3 H 2086. CHF2 H F H Br H H 2087. CHF2 H Me Me H H H 2088. CHF2 H F F F F F 2089. CHF2 H F H H H OMe 2090. CHF2 H Cl H F H H 2091. CHF2 H NO2 H Cl H H 2092. CHF2 H NO2 H H Me H 2093. CHF2 H F H H H I 2094. CHF2 H F H H H Br 2095. CHF2 H Br H H H Br 2096. CHF2 H Cl H H H Me 2097. CHF2 H Cl H H H OCHF2 2098. CHF2 H Cl H H H OMe 2099. CHF2 H Me H H H OMe 2100. CHF2 H OEt H H H CF3 2101. CHF2 H OC(O)Me H H H H 2102. CHF2 H OEt H H H Me 2103. CHF2 H Me Me H H Me 2104. CHF2 H Cl H H H C(O)OMe 2105. CHF2 H Cl H H OMe H 2106. CHF2 H F F H F F 2107. CHF2 H Cl H H F H 2108. CHF2 H F H H F Cl 2109. CHF2 H F H H Cl H 2110. CHF2 H Cl H H CF3 H 2111. CHF2 H Cl Me H H H 2112. CHF2 H OCHF2 H H H H 2113. CHF2 H OCH2CF3 H H H H 2114. CHF2 H CF3 H H H OCHF2 2115. CHF2 H CF3 H H H OCH2CF3 2116. CHF2 H Me H H H Me 2117. CHF2 H Cl H H H F 2118. CHF2 H F H F H H 2119. CHF2 H F Me H H Cl 2120. CHF2 H F H H OMe H 2121. CHF2 H Cl H OCH2O H 2122. CHF2 H Me H H F H 2123. CHF2 H OCF3 H H H H 2124. CHF2 H F F H H H 2125. CHF2 H OMe H H Cl H 2126. Cl Cl H H H H H 2127. Cl Cl F H H H H 2128. Cl Cl F H H F H 2129. Cl Cl F H H H F 2130. Cl Cl F Me H H F 2131. Cl Cl F H H H Cl 2132. Cl Cl CF3 H H H H 2133. Cl Cl Me H H H H 2134. Cl Cl F H H H CF3 2135. Cl Cl F CF3 H H F 2136. Cl Cl Br H H H H 2137. Cl Cl I H H H H 2138. Cl Cl Cl H H H H 2139. Cl Cl Cl H Cl H H 2140. Cl Cl Cl H H H Cl 2141. Cl Cl H Cl Cl H H 2142. Cl Cl Cl Cl Cl H H 2143. Cl Cl Cl Cl H Cl H 2144. Cl Cl Cl Cl Cl H Cl 2145. Cl Cl Cl Cl Cl Cl H 2146. Cl Cl Cl Cl Cl Cl Cl 2147. Cl Cl Cl Cl H H Cl 2148. Cl Cl Cl H Cl Cl H 2149. Cl Cl Cl H H Cl Cl 2150. Cl Cl H Cl Cl Cl H 2151. Cl Cl NO2 H H H H 2152. Cl Cl H Cl H H H 2153. Cl Cl H H Cl H H 2154. Cl Cl Cl H Cl H Cl 2155. Cl Cl Cl Cl H H H 2156. Cl Cl Cl H H Cl H 2157. Cl Cl H Cl H Cl H 2158. Cl Cl H OMe H H H 2159. Cl Cl C(O)OMe H H H H 2160. Cl Cl F Cl H H H 2161. Cl Cl F Me H H H 2162. Cl Cl H Me H H H 2163. Cl Cl OMe H H H H 2164. Cl Cl F F F H H 2165. Cl Cl F F H F H 2166. Cl Cl H F F F H 2167. Cl Cl F H F F H 2168. Cl Cl Me H Me H H 2169. Cl Cl Me H H Me H 2170. Cl Cl F H H CF3 H 2171. Cl Cl F H Br H H 2172. Cl Cl Me Me H H H 2173. Cl Cl F F F F F 2174. Cl Cl F H H H OMe 2175. Cl Cl Cl H F H H 2176. Cl Cl NO2 H Cl H H 2177. Cl Cl NO2 H H Me H 2178. Cl Cl F H H H I 2179. Cl Cl F H H H Br 2180. Cl Cl Br H H H Br 2181. Cl Cl Cl H H H Me 2182. Cl Cl Cl H H H OCHF2 2183. Cl Cl Cl H H H OMe 2184. Cl Cl Me H H H OMe 2185. Cl Cl OEt H H H CF3 2186. Cl Cl OC(O)Me H H H H 2187. Cl Cl OEt H H H Me 2188. Cl Cl Me Me H H Me 2189. Cl Cl Cl H H H C(O)OMe 2190. Cl Cl Cl H H OMe H 2191. Cl Cl F F H F F 2192. Cl Cl Cl H H F H 2193. Cl Cl F H H F Cl 2194. Cl Cl F H H Cl H 2195. Cl Cl Cl H H CF3 H 2196. Cl Cl Cl Me H H H 2197. Cl Cl OCHF2 H H H H 2198. Cl Cl OCH2CF3 H H H H 2199. Cl Cl CF3 H H H OCHF2 2200. Cl Cl CF3 H H H OCH2CF3 2201. Cl Cl Me H H H Me 2202. Cl Cl Cl H H H F 2203. Cl Cl F H F H H 2204. Cl Cl F Me H H Cl 2205. Cl Cl F H H OMe H 2206. Cl Cl Cl H OCH2O H 2207. Cl Cl Me H H F H 2208. Cl Cl OCF3 H H H H 2209. Cl Cl F F H H H 2210. Cl Cl OMe H H Cl H 2211. Me Cl H H H H H 2212. Me Cl F H H H H 2213. Me Cl F H H F H 2214. Me Cl F H H H F 2215. Me Cl F Me H H F 2216. Me Cl F H H H Cl 2217. Me Cl CF3 H H H H 2218. Me Cl Me H H H H 2219. Me Cl F H H H CF3 2220. Me Cl F CF3 H H F 2221. Me Cl Br H H H H 2222. Me Cl I H H H H 2223. Me Cl Cl H H H H 2224. Me Cl Cl H Cl H H 2225. Me Cl Cl H H H Cl 2226. Me Cl H Cl Cl H H 2227. Me Cl Cl Cl Cl H H 2228. Me Cl Cl Cl H Cl H 2229. Me Cl Cl Cl Cl H Cl 2230. Me Cl Cl Cl Cl Cl H 2231. Me Cl Cl Cl Cl Cl Cl 2232. Me Cl Cl Cl H H Cl 2233. Me Cl Cl H Cl Cl H 2234. Me Cl Cl H H Cl Cl 2235. Me Cl H Cl Cl Cl H 2236. Me Cl NO2 H H H H 2237. Me Cl H Cl H H H 2238. Me Cl H H Cl H H 2239. Me Cl Cl H Cl H Cl 2240. Me Cl Cl Cl H H H 2241. Me Cl Cl H H Cl H 2242. Me Cl H Cl H Cl H 2243. Me Cl H OMe H H H 2244. Me Cl C(O)OMe H H H H 2245. Me Cl F Cl H H H 2246. Me Cl F Me H H H 2247. Me Cl H Me H H H 2248. Me Cl OMe H H H H 2249. Me Cl F F F H H 2250. Me Cl F F H F H 2251. Me Cl H F F F H 2252. Me Cl F H F F H 2253. Me Cl Me H Me H H 2254. Me Cl Me H H Me H 2255. Me Cl F H H CF3 H 2256. Me Cl F H Br H H 2257. Me Cl Me Me H H H 2258. Me Cl F F F F F 2259. Me Cl F H H H OMe 2260. Me Cl Cl H F H H 2261. Me Cl NO2 H Cl H H 2262. Me Cl NO2 H H Me H 2263. Me Cl F H H H I 2264. Me Cl F H H H Br 2265. Me Cl Br H H H Br 2266. Me Cl Cl H H H Me 2267. Me Cl Cl H H H OCHF2 2268. Me Cl Cl H H H OMe 2269. Me Cl Me H H H OMe 2270. Me Cl OEt H H H CF3 2271. Me Cl OC(O)Me H H H H 2272. Me Cl OEt H H H Me 2273. Me Cl Me Me H H Me 2274. Me Cl Cl H H H C(O)OMe 2275. Me Cl Cl H H OMe H 2276. Me Cl F F H F F 2277. Me Cl Cl H H F H 2278. Me Cl F H H F Cl 2279. Me Cl F H H Cl H 2280. Me Cl Cl H H CF3 H 2281. Me Cl Cl Me H H H 2282. Me Cl OCHF2 H H H H 2283. Me Cl OCH2CF3 H H H H 2284. Me Cl CF3 H H H OCHF2 2285. Me Cl CF3 H H H OCH2CF3 2286. Me Cl Me H H H Me 2287. Me Cl Cl H H H F 2288. Me Cl F H F H H 2289. Me Cl F Me H H Cl 2290. Me Cl F H H OMe H 2291. Me Cl Cl H OCH2O H 2292. Me Cl Me H H F H 2293. Me Cl OCF3 H H H H 2294. Me Cl F F H H H 2295. Me Cl OMe H H Cl H 2296. Cl Me H H H H H 2297. Cl Me F H H H H 2298. Cl Me F H H F H 2299. Cl Me F H H H F 2300. Cl Me F Me H H F 2301. Cl Me F H H H Cl 2302. Cl Me CF3 H H H H 2303. Cl Me Me H H H H 2304. Cl Me F H H H CF3 2305. Cl Me F CF3 H H F 2306. Cl Me Br H H H H 2307. Cl Me I H H H H 2308. Cl Me Cl H H H H 2309. Cl Me Cl H Cl H H 2310. Cl Me Cl H H H Cl 2311. Cl Me H Cl Cl H H 2312. Cl Me Cl Cl Cl H H 2313. Cl Me Cl Cl H Cl H 2314. Cl Me Cl Cl Cl H Cl 2315. Cl Me Cl Cl Cl Cl H 2316. Cl Me Cl Cl Cl Cl Cl 2317. Cl Me Cl Cl H H Cl 2318. Cl Me Cl H Cl Cl H 2319. Cl Me Cl H H Cl Cl 2320. Cl Me H Cl Cl Cl H 2321. Cl Me NO2 H H H H 2322. Cl Me H Cl H H H 2323. Cl Me H H Cl H H 2324. Cl Me Cl H Cl H Cl 2325. Cl Me Cl Cl H H H 2326. Cl Me Cl H H Cl H 2327. Cl Me H Cl H Cl H 2328. Cl Me H OMe H H H 2329. Cl Me C(O)OMe H H H H 2330. Cl Me F Cl H H H 2331. Cl Me F Me H H H 2332. Cl Me H Me H H H 2333. Cl Me OMe H H H H 2334. Cl Me F F F H H 2335. Cl Me F F H F H 2336. Cl Me H F F F H 2337. Cl Me F H F F H 2338. Cl Me Me H Me H H 2339. Cl Me Me H H Me H 2340. Cl Me F H H CF3 H 2341. Cl Me F H Br H H 2342. Cl Me Me Me H H H 2343. Cl Me F F F F F 2344. Cl Me F H H H OMe 2345. Cl Me Cl H F H H 2346. Cl Me NO2 H Cl H H 2347. Cl Me NO2 H H Me H 2348. Cl Me F H H H I 2349. Cl Me F H H H Br 2350. Cl Me Br H H H Br 2351. Cl Me Cl H H H Me 2352. Cl Me Cl H H H OCHF2 2353. Cl Me Cl H H H OMe 2354. Cl Me Me H H H OMe 2355. Cl Me OEt H H H CF3 2356. Cl Me OC(O)Me H H H H 2357. Cl Me OEt H H H Me 2358. Cl Me Me Me H H Me 2359. Cl Me Cl H H H C(O)OMe 2360. Cl Me Cl H H OMe H 2361. Cl Me F F H F F 2362. Cl Me Cl H H F H 2363. Cl Me F H H F Cl 2364. Cl Me F H H Cl H 2365. Cl Me Cl H H CF3 H 2366. Cl Me Cl Me H H H 2367. Cl Me OCHF2 H H H H 2368. Cl Me OCH2CF3 H H H H 2369. Cl Me CF3 H H H OCHF2 2370. Cl Me CF3 H H H OCH2CF3 2371. Cl Me Me H H H Me 2372. Cl Me Cl H H H F 2373. Cl Me F H F H H 2374. Cl Me F Me H H Cl 2375. Cl Me F H H OMe H 2376. Cl Me Cl H OCH2O H 2377. Cl Me Me H H F H 2378. Cl Me OCF3 H H H H 2379. Cl Me F F H H H 2380. Cl Me OMe H H Cl H

TABLE 3 Compounds of the formula Ib-S (Ib-S) Ex. No. R11 R12 R6 R7 R8 2381. H H CF3 Ph Cl 2382. H H CF3 tBu Cl 2383. H H CF3 CHF2 Cl 2384. H H Cl CHF2 CF3 2385. H H CF3 Me OMe 2386. H H CF3 Me CN 2387. H H Cl Et Cl 2388. H H CHF2 Me Cl 2389. H H Me Me Me 2390. H H Me Me Cl 2391. H H Cl Me Cl 2392. H H CF3 Me Cl 2393. H H Cl Me CF3 2394. H H CF3 Me F 2395. H H OMe Me CF3 2396. H H CF3 Me OEt 2397. H H CF3 Me OCHF2 2398. H H OCHF2 Me CF3 2399. H H CF3 Me OCH2CHF2 2400. H H CF3 Me OCH2CF3 2401. H H CF3 Me OCH2CN 2402. H H CF3 Me SO2Me 2403. H H CF3 Me SEt 2404. H H CF3 Me Me 2405. H H CF3 Me Et 2406. H H CF3 Et Cl 2407. H H Cl Et CF3 2408. H H CF3 iPr Cl 2409. H H Cl iPr CF3 2410. H H CF3 tBu Cl 2411. H H Cl tBu CF3 2412. H H CF3 cPen Cl 2413. H H Cl cPen CF3 2414. H H CF3 CH2cPr Cl 2415. H H Cl CH2cPr CF3 2416. H H CF3 CH2CH═CH2 Cl 2417. H H Cl CH2CH═CH2 CF3 2418. H H CF3 CHF2 OMe 2419. H H OMe CHF2 CF3 2420. H H CF3 CH2CF3 Cl 2421. H H Cl CH2CF3 CF3 2422. H H CF3 CH2OMe Cl 2423. H H Cl CH2OMe CF3 2424. H H CF3 CH2CN Cl 2425. H H Me Ph Me 2426. H H Me Ph Cl 2427. H H Et Ph Cl 2428. H H Pr Ph Cl 2429. H H iPr Ph Cl 2430. H H CF3 Ph Cl 2431. H H CF3 Ph Me 2432. H H CF3 Ph CF3 2433. H H CF3 Ph F 2434. H H CF3 Ph OMe 2435. H H CF3 Ph OEt 2436. H H CF3 Ph OCHF2 2437. H H CF3 Ph CN 2438. H H CF3 Ph(4-Cl) Cl 2439. H H Me Me OCH2CF3 2440. H H CF3 Me 2441. H H CF3 Me H 2442. H H CF3 Me OCH2CH2OMe 2443. H H CF3 Me SMe 2444. H H CF3 Me OCH2CH2CH2F 2445. H H CF3 Me OCH(CH2F)2 2446. H H CF3 Me OCH2CF2CHF2 2447. H H CF3 Me OCH2CF═CH2 2448. H H CF3 Me OCH(Me)CF3 2449. H H CF3 Me OCH(Me)CH2F 2450. H H OCH2CF3 Me CF3 2451. H H OCH2CF3 Me CHF2 2452. H H CHF2 Me CHF2 2453. H H CF3 Me CHF2 2454. H H Cl Me OCHF2 2455. H H Br Me OCHF2 2456. H H Br Me CF3 2457. F H CF3 Ph Cl 2458. F H CF3 tBu Cl 2459. F H CF3 CHF2 Cl 2460. F H Cl CHF2 CF3 2461. F H CF3 Me OMe 2462. F H CF3 Me CN 2463. F H Cl Et Cl 2464. F H CHF2 Me Cl 2465. F H Me Me Me 2466. F H Me Me Cl 2467. F H Cl Me Cl 2468. F H CF3 Me Cl 2469. F H Cl Me CF3 2470. F H CF3 Me F 2471. F H OMe Me CF3 2472. F H CF3 Me OEt 2473. F H CF3 Me OCHF2 2474. F H OCHF2 Me CF3 2475. F H CF3 Me OCH2CHF2 2476. F H CF3 Me OCH2CF3 2477. F H CF3 Me OCH2CN 2478. F H CF3 Me SO2Me 2479. F H CF3 Me SEt 2480. F H CF3 Me Me 2481. F H CF3 Me Et 2482. F H CF3 Et Cl 2483. F H Cl Et CF3 2484. F H CF3 iPr Cl 2485. F H Cl iPr CF3 2486. F H CF3 tBu Cl 2487. F H Cl tBu CF3 2488. F H CF3 cPen Cl 2489. F H Cl cPen CF3 2490. F H CF3 CH2cPr Cl 2491. F H Cl CH2cPr CF3 2492. F H CF3 CH2CH═CH2 Cl 2493. F H Cl CH2CH═CH2 CF3 2494. F H CF3 CHF2 OMe 2495. F H OMe CHF2 CF3 2496. F H CF3 CH2CF3 Cl 2497. F H Cl CH2CF3 CF3 2498. F H CF3 CH2OMe Cl 2499. F H Cl CH2OMe CF3 2500. F H CF3 CH2CN Cl 2501. F H Me Ph Me 2502. F H Me Ph Cl 2503. F H Et Ph Cl 2504. F H Pr Ph Cl 2505. F H iPr Ph Cl 2506. F H CF3 Ph Cl 2507. F H CF3 Ph Me 2508. F H CF3 Ph CF3 2509. F H CF3 Ph F 2510. F H CF3 Ph OMe 2511. F H CF3 Ph OEt 2512. F H CF3 Ph OCHF2 2513. F H CF3 Ph CN 2514. F H CF3 Ph(4-Cl) Cl 2515. F H Me Me OCH2CF3 2516. F H CF3 Me 2517. F H CF3 Me H 2518. F H CF3 Me OCH2CH2OMe 2519. F H CF3 Me SMe 2520. F H CF3 Me OCH2CH2CH2F 2521. F H CF3 Me OCH(CH2F)2 2522. F H CF3 Me OCH2CF2CHF2 2523. F H CF3 Me OCH2CF═CH2 2524. F H CF3 Me OCH(Me)CF3 2525. F H CF3 Me OCH(Me)CH2F 2526. F H OCH2CF3 Me CF3 2527. F H OCH2CF3 Me CHF2 2528. F H CHF2 Me CHF2 2529. F H CF3 Me CHF2 2530. F H Cl Me OCHF2 2531. F H Br Me OCHF2 2532. F H Br Me CF3 2533. F H CF3 Me CF3 2534. F H CHF2 Me OCHF2 2535. F H CHF2 Me CF3 2536. F H CF2CF3 Me CF3 2537. F H CF3 Me CF2CF3 2538. F H CHF2 Me OCH2CF3 2539. Cl H CF3 Ph Cl 2540. Cl H CF3 tBu Cl 2541. Cl H CF3 CHF2 Cl 2542. Cl H Cl CHF2 CF3 2543. Cl H CF3 Me OMe 2544. Cl H CF3 Me CN 2545. Cl H Cl Et Cl 2546. Cl H CHF2 Me Cl 2547. Cl H Me Me Me 2548. Cl H Me Me Cl 2549. Cl H Cl Me Cl 2550. Cl H CF3 Me Cl 2551. Cl H Cl Me CF3 2552. Cl H CF3 Me F 2553. Cl H OMe Me CF3 2554. Cl H CF3 Me OEt 2555. Cl H CF3 Me OCHF2 2556. Cl H OCHF2 Me CF3 2557. Cl H CF3 Me OCH2CHF2 2558. Cl H CF3 Me OCH2CF3 2559. Cl H CF3 Me OCH2CN 2560. Cl H CF3 Me SO2Me 2561. Cl H CF3 Me SEt 2562. Cl H CF3 Me Me 2563. Cl H CF3 Me Et 2564. Cl H CF3 Et Cl 2565. Cl H Cl Et CF3 2566. Cl H CF3 iPr Cl 2567. Cl H Cl iPr CF3 2568. Cl H CF3 tBu Cl 2569. Cl H Cl tBu CF3 2570. Cl H CF3 cPen Cl 2571. Cl H Cl cPen CF3 2572. Cl H CF3 CH2cPr Cl 2573. Cl H Cl CH2cPr CF3 2574. Cl H CF3 CH2CH═CH2 Cl 2575. Cl H Cl CH2CH═CH2 CF3 2576. Cl H CF3 CHF2 OMe 2577. Cl H OMe CHF2 CF3 2578. Cl H CF3 CH2CF3 Cl 2579. Cl H Cl CH2CF3 CF3 2580. Cl H CF3 CH2OMe Cl 2581. Cl H Cl CH2OMe CF3 2582. Cl H CF3 CH2CN Cl 2583. Cl H Me Ph Me 2584. Cl H Me Ph Cl 2585. Cl H Et Ph Cl 2586. Cl H Pr Ph Cl 2587. Cl H iPr Ph Cl 2588. Cl H CF3 Ph Cl 2589. Cl H CF3 Ph Me 2590. Cl H CF3 Ph CF3 2591. Cl H CF3 Ph F 2592. Cl H CF3 Ph OMe 2593. Cl H CF3 Ph OEt 2594. Cl H CF3 Ph OCHF2 2595. Cl H CF3 Ph CN 2596. Cl H CF3 Ph(4-Cl) Cl 2597. Cl H Me Me OCH2CF3 2598. Cl H CF3 Me 2599. Cl H CF3 Me H 2600. Cl H CF3 Me OCH2CH2OMe 2601. Cl H CF3 Me SMe 2602. Cl H CF3 Me OCH2CH2CH2F 2603. Cl H CF3 Me OCH(CH2F)2 2604. Cl H CF3 Me OCH2CF2CHF2 2605. Cl H CF3 Me OCH2CF═CH2 2606. Cl H CF3 Me OCH(Me)CF3 2607. Cl H CF3 Me OCH(Me)CH2F 2608. Cl H OCH2CF3 Me CF3 2609. Cl H OCH2CF3 Me CHF2 2610. Cl H CHF2 Me CHF2 2611. Cl H CF3 Me CHF2 2612. Cl H Cl Me OCHF2 2613. Cl H Br Me OCHF2 2614. Cl H Br Me CF3 2615. Cl H CF3 Me CF3 2616. Cl H CHF2 Me OCHF2 2617. Cl H CHF2 Me CF3 2618. Cl H CF2CF3 Me CF3 2619. Cl H CF3 Me CF2CF3 2620. Cl H CHF2 Me OCH2CF3 2621. Br H CF3 Ph Cl 2622. Br H CF3 tBu Cl 2623. Br H CF3 CHF2 Cl 2624. Br H Cl CHF2 CF3 2625. Br H CF3 Me OMe 2626. Br H CF3 Me CN 2627. Br H Cl Et Cl 2628. Br H CHF2 Me Cl 2629. Br H Me Me Me 2630. Br H Me Me Cl 2631. Br H Cl Me Cl 2632. Br H CF3 Me Cl 2633. Br H Cl Me CF3 2634. Br H CF3 Me F 2635. Br H OMe Me CF3 2636. Br H CF3 Me OEt 2637. Br H CF3 Me OCHF2 2638. Br H OCHF2 Me CF3 2639. Br H CF3 Me OCH2CHF2 2640. Br H CF3 Me OCH2CF3 2641. Br H CF3 Me OCH2CN 2642. Br H CF3 Me SO2Me 2643. Br H CF3 Me SEt 2644. Br H CF3 Me Me 2645. Br H CF3 Me Et 2646. Br H CF3 Et Cl 2647. Br H Cl Et CF3 2648. Br H CF3 iPr Cl 2649. Br H Cl iPr CF3 2650. Br H CF3 tBu Cl 2651. Br H Cl tBu CF3 2652. Br H CF3 cPen Cl 2653. Br H Cl cPen CF3 2654. Br H CF3 CH2cPr Cl 2655. Br H Cl CH2cPr CF3 2656. Br H CF3 CH2CH═CH2 Cl 2657. Br H Cl CH2CH═CH2 CF3 2658. Br H CF3 CHF2 OMe 2659. Br H OMe CHF2 CF3 2660. Br H CF3 CH2CF3 Cl 2661. Br H Cl CH2CF3 CF3 2662. Br H CF3 CH2OMe Cl 2663. Br H Cl CH2OMe CF3 2664. Br H CF3 CH2CN Cl 2665. Br H Me Ph Me 2666. Br H Me Ph Cl 2667. Br H Et Ph Cl 2668. Br H Pr Ph Cl 2669. Br H iPr Ph Cl 2670. Br H CF3 Ph Cl 2671. Br H CF3 Ph Me 2672. Br H CF3 Ph CF3 2673. Br H CF3 Ph F 2674. Br H CF3 Ph OMe 2675. Br H CF3 Ph OEt 2676. Br H CF3 Ph OCHF2 2677. Br H CF3 Ph CN 2678. Br H CF3 Ph(4-Cl) Cl 2679. Br H Me Me OCH2CF3 2680. Br H CF3 Me 2681. Br H CF3 Me H 2682. Br H CF3 Me OCH2CH2OMe 2683. Br H CF3 Me SMe 2684. Br H CF3 Me OCH2CH2CH2F 2685. Br H CF3 Me OCH(CH2F)2 2686. Br H CF3 Me OCH2CF2CHF2 2687. Br H CF3 Me OCH2CF═CH2 2688. Br H CF3 Me OCH(Me)CF3 2689. Br H CF3 Me OCH(Me)CH2F 2690. Br H OCH2CF3 Me CF3 2691. Br H OCH2CF3 Me CHF2 2692. Br H CHF2 Me CHF2 2693. Br H CF3 Me CHF2 2694. Br H Cl Me OCHF2 2695. Br H Br Me OCHF2 2696. Br H Br Me CF3 2697. Br H CF3 Me CF3 2698. Br H CHF2 Me OCHF2 2699. Br H CHF2 Me CF3 2700. Br H CF2CF3 Me CF3 2701. Br H CF3 Me CF2CF3 2702. Br H CHF2 Me OCH2CF3 2703. I H CF3 Ph Cl 2704. I H CF3 tBu Cl 2705. I H CF3 CHF2 Cl 2706. I H Cl CHF2 CF3 2707. I H CF3 Me OMe 2708. I H CF3 Me CN 2709. I H Cl Et Cl 2710. I H CHF2 Me Cl 2711. I H Me Me Me 2712. I H Me Me Cl 2713. I H Cl Me Cl 2714. I H CF3 Me Cl 2715. I H Cl Me CF3 2716. I H CF3 Me F 2717. I H OMe Me CF3 2718. I H CF3 Me OEt 2719. I H CF3 Me OCHF2 2720. I H OCHF2 Me CF3 2721. I H CF3 Me OCH2CHF2 2722. I H CF3 Me OCH2CF3 2723. I H CF3 Me OCH2CN 2724. I H CF3 Me SO2Me 2725. I H CF3 Me SEt 2726. I H CF3 Me Me 2727. I H CF3 Me Et 2728. I H CF3 Et Cl 2729. I H Cl Et CF3 2730. I H CF3 iPr Cl 2731. I H Cl iPr CF3 2732. I H CF3 tBu Cl 2733. I H Cl tBu CF3 2734. I H CF3 cPen Cl 2735. I H Cl cPen CF3 2736. I H CF3 CH2cPr Cl 2737. I H Cl CH2cPr CF3 2738. I H CF3 CH2CH═CH2 Cl 2739. I H Cl CH2CH═CH2 CF3 2740. I H CF3 CHF2 OMe 2741. I H OMe CHF2 CF3 2742. I H CF3 CH2CF3 Cl 2743. I H Cl CH2CF3 CF3 2744. I H CF3 CH2OMe Cl 2745. I H Cl CH2OMe CF3 2746. I H CF3 CH2CN Cl 2747. I H Me Ph Me 2748. I H Me Ph Cl 2749. I H Et Ph Cl 2750. I H Pr Ph Cl 2751. I H iPr Ph Cl 2752. I H CF3 Ph Cl 2753. I H CF3 Ph Me 2754. I H CF3 Ph CF3 2755. I H CF3 Ph F 2756. I H CF3 Ph OMe 2757. I H CF3 Ph OEt 2758. I H CF3 Ph OCHF2 2759. I H CF3 Ph CN 2760. I H CF3 Ph(4-Cl) Cl 2761. I H Me Me OCH2CF3 2762. I H CF3 Me 2763. I H CF3 Me H 2764. I H CF3 Me OCH2CH2OMe 2765. I H CF3 Me SMe 2766. I H CF3 Me OCH2CH2CH2F 2767. I H CF3 Me OCH(CH2F)2 2768. I H CF3 Me OCH2CF2CHF2 2769. I H CF3 Me OCH2CF═CH2 2770. I H CF3 Me OCH(Me)CF3 2771. I H CF3 Me OCH(Me)CH2F 2772. I H OCH2CF3 Me CF3 2773. I H OCH2CF3 Me CHF2 2774. I H CHF2 Me CHF2 2775. I H CF3 Me CHF2 2776. I H Cl Me OCHF2 2777. I H Br Me OCHF2 2778. I H Br Me CF3 2779. I H CF3 Me CF3 2780. I H CHF2 Me OCHF2 2781. I H CHF2 Me CF3 2782. I H CF2CF3 Me CF3 2783. I H CF3 Me CF2CF3 2784. I H CHF2 Me OCH2CF3 2785. H Cl CF3 Ph Cl 2786. H Cl CF3 tBu Cl 2787. H Cl CF3 CHF2 Cl 2788. H Cl Cl CHF2 CF3 2789. H Cl CF3 Me OMe 2790. H Cl CF3 Me CN 2791. H Cl Cl Et Cl 2792. H Cl CHF2 Me Cl 2793. H Cl Me Me Me 2794. H Cl Me Me Cl 2795. H Cl Cl Me Cl 2796. H Cl CF3 Me Cl 2797. H Cl Cl Me CF3 2798. H Cl CF3 Me F 2799. H Cl OMe Me CF3 2800. H Cl CF3 Me OEt 2801. H Cl CF3 Me OCHF2 2802. H Cl OCHF2 Me CF3 2803. H Cl CF3 Me OCH2CHF2 2804. H Cl CF3 Me OCH2CF3 2805. H Cl CF3 Me OCH2CN 2806. H Cl CF3 Me SO2Me 2807. H Cl CF3 Me SEt 2808. H Cl CF3 Me Me 2809. H Cl CF3 Me Et 2810. H Cl CF3 Et Cl 2811. H Cl Cl Et CF3 2812. H Cl CF3 iPr Cl 2813. H Cl Cl iPr CF3 2814. H Cl CF3 tBu Cl 2815. H Cl Cl tBu CF3 2816. H Cl CF3 cPen Cl 2817. H Cl Cl cPen CF3 2818. H Cl CF3 CH2cPr Cl 2819. H Cl Cl CH2cPr CF3 2820. H Cl CF3 CH2CH═CH2 Cl 2821. H Cl Cl CH2CH═CH2 CF3 2822. H Cl CF3 CHF2 OMe 2823. H Cl OMe CHF2 CF3 2824. H Cl CF3 CH2CF3 Cl 2825. H Cl Cl CH2CF3 CF3 2826. H Cl CF3 CH2OMe Cl 2827. H Cl Cl CH2OMe CF3 2828. H Cl CF3 CH2CN Cl 2829. H Cl Me Ph Me 2830. H Cl Me Ph Cl 2831. H Cl Et Ph Cl 2832. H Cl Pr Ph Cl 2833. H Cl iPr Ph Cl 2834. H Cl CF3 Ph Cl 2835. H Cl CF3 Ph Me 2836. H Cl CF3 Ph CF3 2837. H Cl CF3 Ph F 2838. H Cl CF3 Ph OMe 2839. H Cl CF3 Ph OEt 2840. H Cl CF3 Ph OCHF2 2841. H Cl CF3 Ph CN 2842. H Cl CF3 Ph(4-Cl) Cl 2843. H Cl Me Me OCH2CF3 2844. H Cl CF3 Me 2845. H Cl CF3 Me H 2846. H Cl CF3 Me OCH2CH2OMe 2847. H Cl CF3 Me SMe 2848. H Cl CF3 Me OCH2CH2CH2F 2849. H Cl CF3 Me OCH(CH2F)2 2850. H Cl CF3 Me OCH2CF2CHF2 2851. H Cl CF3 Me OCH2CF═CH2 2852. H Cl CF3 Me OCH(Me)CF3 2853. H Cl CF3 Me OCH(Me)CH2F 2854. H Cl OCH2CF3 Me CF3 2855. H Cl OCH2CF3 Me CHF2 2856. H Cl CHF2 Me CHF2 2857. H Cl CF3 Me CHF2 2858. H Cl Cl Me OCHF2 2859. H Cl Br Me OCHF2 2860. H Cl Br Me CF3 2861. H Br CF3 Ph Cl 2862. H Br CF3 tBu Cl 2863. H Br CF3 CHF2 Cl 2864. H Br Cl CHF2 CF3 2865. H Br CF3 Me OMe 2866. H Br CF3 Me CN 2867. H Br Cl Et Cl 2868. H Br CHF2 Me Cl 2869. H Br Me Me Me 2870. H Br Me Me Cl 2871. H Br Cl Me Cl 2872. H Br CF3 Me Cl 2873. H Br Cl Me CF3 2874. H Br CF3 Me F 2875. H Br OMe Me CF3 2876. H Br CF3 Me OEt 2877. H Br CF3 Me OCHF2 2878. H Br OCHF2 Me CF3 2879. H Br CF3 Me OCH2CHF2 2880. H Br CF3 Me OCH2CF3 2881. H Br CF3 Me OCH2CN 2882. H Br CF3 Me SO2Me 2883. H Br CF3 Me SEt 2884. H Br CF3 Me Me 2885. H Br CF3 Me Et 2886. H Br CF3 Et Cl 2887. H Br Cl Et CF3 2888. H Br CF3 iPr Cl 2889. H Br Cl iPr CF3 2890. H Br CF3 tBu Cl 2891. H Br Cl tBu CF3 2892. H Br CF3 cPen Cl 2893. H Br Cl cPen CF3 2894. H Br CF3 CH2cPr Cl 2895. H Br Cl CH2cPr CF3 2896. H Br CF3 CH2CH═CH2 Cl 2897. H Br Cl CH2CH═CH2 CF3 2898. H Br CF3 CHF2 OMe 2899. H Br OMe CHF2 CF3 2900. H Br CF3 CH2CF3 Cl 2901. H Br Cl CH2CF3 CF3 2902. H Br CF3 CH2OMe Cl 2903. H Br Cl CH2OMe CF3 2904. H Br CF3 CH2CN Cl 2905. H Br Me Ph Me 2906. H Br Me Ph Cl 2907. H Br Et Ph Cl 2908. H Br Pr Ph Cl 2909. H Br iPr Ph Cl 2910. H Br CF3 Ph Cl 2911. H Br CF3 Ph Me 2912. H Br CF3 Ph CF3 2913. H Br CF3 Ph F 2914. H Br CF3 Ph OMe 2915. H Br CF3 Ph OEt 2916. H Br CF3 Ph OCHF2 2917. H Br CF3 Ph CN 2918. H Br CF3 Ph(4-Cl) Cl 2919. H Br Me Me OCH2CF3 2920. H Br CF3 Me 2921. H Br CF3 Me H 2922. H Br CF3 Me OCH2CH2OMe 2923. H Br CF3 Me SMe 2924. H Br CF3 Me OCH2CH2CH2F 2925. H Br CF3 Me OCH(CH2F)2 2926. H Br CF3 Me OCH2CF2CHF2 2927. H Br CF3 Me OCH2CF═CH2 2928. H Br CF3 Me OCH(Me)CF3 2929. H Br CF3 Me OCH(Me)CH2F 2930. H Br OCH2CF3 Me CF3 2931. H Br OCH2CF3 Me CHF2 2932. H Br CHF2 Me CHF2 2933. H Br CF3 Me CHF2 2934. H Br Cl Me OCHF2 2935. H Br Br Me OCHF2 2936. H Br Br Me CF3 2937. Me H CF3 Ph Cl 2938. Me H CF3 tBu Cl 2939. Me H CF3 CHF2 Cl 2940. Me H Cl CHF2 CF3 2941. Me H CF3 Me OMe 2942. Me H CF3 Me CN 2943. Me H Cl Et Cl 2944. Me H CHF2 Me Cl 2945. Me H Me Me Me 2946. Me H Me Me Cl 2947. Me H Cl Me Cl 2948. Me H CF3 Me Cl 2949. Me H Cl Me CF3 2950. Me H CF3 Me F 2951. Me H OMe Me CF3 2952. Me H CF3 Me OEt 2953. Me H CF3 Me OCHF2 2954. Me H OCHF2 Me CF3 2955. Me H CF3 Me OCH2CHF2 2956. Me H CF3 Me OCH2CF3 2957. Me H CF3 Me OCH2CN 2958. Me H CF3 Me SO2Me 2959. Me H CF3 Me SEt 2960. Me H CF3 Me Me 2961. Me H CF3 Me Et 2962. Me H CF3 Et Cl 2963. Me H Cl Et CF3 2964. Me H CF3 iPr Cl 2965. Me H Cl iPr CF3 2966. Me H CF3 tBu Cl 2967. Me H Cl tBu CF3 2968. Me H CF3 cPen Cl 2969. Me H Cl cPen CF3 2970. Me H CF3 CH2cPr Cl 2971. Me H Cl CH2cPr CF3 2972. Me H CF3 CH2CH═CH2 Cl 2973. Me H Cl CH2CH═CH2 CF3 2974. Me H CF3 CHF2 OMe 2975. Me H OMe CHF2 CF3 2976. Me H CF3 CH2CF3 Cl 2977. Me H Cl CH2CF3 CF3 2978. Me H CF3 CH2OMe Cl 2979. Me H Cl CH2OMe CF3 2980. Me H CF3 CH2CN Cl 2981. Me H Me Ph Me 2982. Me H Me Ph Cl 2983. Me H Et Ph Cl 2984. Me H Pr Ph Cl 2985. Me H iPr Ph Cl 2986. Me H CF3 Ph Cl 2987. Me H CF3 Ph Me 2988. Me H CF3 Ph CF3 2989. Me H CF3 Ph F 2990. Me H CF3 Ph OMe 2991. Me H CF3 Ph OEt 2992. Me H CF3 Ph OCHF2 2993. Me H CF3 Ph CN 2994. Me H CF3 Ph(4-Cl) Cl 2995. Me H Me Me OCH2CF3 2996. Me H CF3 Me 2997. Me H CF3 Me H 2998. Me H CF3 Me OCH2CH2OMe 2999. Me H CF3 Me SMe 3000. Me H CF3 Me OCH2CH2CH2F 3001. Me H CF3 Me OCH(CH2F)2 3002. Me H CF3 Me OCH2CF2CHF2 3003. Me H CF3 Me OCH2CF═CH2 3004. Me H CF3 Me OCH(Me)CF3 3005. Me H CF3 Me OCH(Me)CH2F 3006. Me H OCH2CF3 Me CF3 3007. Me H OCH2CF3 Me CHF2 3008. Me H CHF2 Me CHF2 3009. Me H CF3 Me CHF2 3010. Me H Cl Me OCHF2 3011. Me H Br Me OCHF2 3012. Me H Br Me CF3 3013. H Me CF3 Ph Cl 3014. H Me CF3 tBu Cl 3015. H Me CF3 CHF2 Cl 3016. H Me Cl CHF2 CF3 3017. H Me CF3 Me OMe 3018. H Me CF3 Me CN 3019. H Me Cl Et Cl 3020. H Me CHF2 Me Cl 3021. H Me Me Me Me 3022. H Me Me Me Cl 3023. H Me Cl Me Cl 3024. H Me CF3 Me Cl 3025. H Me Cl Me CF3 3026. H Me CF3 Me F 3027. H Me OMe Me CF3 3028. H Me CF3 Me OEt 3029. H Me CF3 Me OCHF2 3030. H Me OCHF2 Me CF3 3031. H Me CF3 Me OCH2CHF2 3032. H Me CF3 Me OCH2CF3 3033. H Me CF3 Me OCH2CN 3034. H Me CF3 Me SO2Me 3035. H Me CF3 Me SEt 3036. H Me CF3 Me Me 3037. H Me CF3 Me Et 3038. H Me CF3 Et Cl 3039. H Me Cl Et CF3 3040. H Me CF3 iPr Cl 3041. H Me Cl iPr CF3 3042. H Me CF3 tBu Cl 3043. H Me Cl tBu CF3 3044. H Me CF3 cPen Cl 3045. H Me Cl cPen CF3 3046. H Me CF3 CH2cPr Cl 3047. H Me Cl CH2cPr CF3 3048. H Me CF3 CH2CH═CH2 Cl 3049. H Me Cl CH2CH═CH2 CF3 3050. H Me CF3 CHF2 OMe 3051. H Me OMe CHF2 CF3 3052. H Me CF3 CH2CF3 Cl 3053. H Me Cl CH2CF3 CF3 3054. H Me CF3 CH2OMe Cl 3055. H Me Cl CH2OMe CF3 3056. H Me CF3 CH2CN Cl 3057. H Me Me Ph Me 3058. H Me Me Ph Cl 3059. H Me Et Ph Cl 3060. H Me Pr Ph Cl 3061. H Me iPr Ph Cl 3062. H Me CF3 Ph Cl 3063. H Me CF3 Ph Me 3064. H Me CF3 Ph CF3 3065. H Me CF3 Ph F 3066. H Me CF3 Ph OMe 3067. H Me CF3 Ph OEt 3068. H Me CF3 Ph OCHF2 3069. H Me CF3 Ph CN 3070. H Me CF3 Ph(4-Cl) Cl 3071. H Me Me Me OCH2CF3 3072. H Me CF3 Me 3073. H Me CF3 Me H 3074. H Me CF3 Me OCH2CH2OMe 3075. H Me CF3 Me SMe 3076. H Me CF3 Me OCH2CH2CH2F 3077. H Me CF3 Me OCH(CH2F)2 3078. H Me CF3 Me OCH2CF2CHF2 3079. H Me CF3 Me OCH2CF═CH2 3080. H Me CF3 Me OCH(Me)CF3 3081. H Me CF3 Me OCH(Me)CH2F 3082. H Me OCH2CF3 Me CF3 3083. H Me OCH2CF3 Me CHF2 3084. H Me CHF2 Me CHF2 3085. H Me CF3 Me CHF2 3086. H Me Cl Me OCHF2 3087. H Me Br Me OCHF2 3088. H Me Br Me CF3 3089. NO2 H CF3 Ph Cl 3090. NO2 H CF3 tBu Cl 3091. NO2 H CF3 CHF2 Cl 3092. NO2 H Cl CHF2 CF3 3093. NO2 H CF3 Me OMe 3094. NO2 H CF3 Me CN 3095. NO2 H Cl Et Cl 3096. NO2 H CHF2 Me Cl 3097. NO2 H Me Me Me 3098. NO2 H Me Me Cl 3099. NO2 H Cl Me Cl 3100. NO2 H CF3 Me Cl 3101. NO2 H Cl Me CF3 3102. NO2 H CF3 Me F 3103. NO2 H OMe Me CF3 3104. NO2 H CF3 Me OEt 3105. NO2 H CF3 Me OCHF2 3106. NO2 H OCHF2 Me CF3 3107. NO2 H CF3 Me OCH2CHF2 3108. NO2 H CF3 Me OCH2CF3 3109. NO2 H CF3 Me OCH2CN 3110. NO2 H CF3 Me SO2Me 3111. NO2 H CF3 Me SEt 3112. NO2 H CF3 Me Me 3113. NO2 H CF3 Me Et 3114. NO2 H CF3 Et Cl 3115. NO2 H Cl Et CF3 3116. NO2 H CF3 iPr Cl 3117. NO2 H Cl iPr CF3 3118. NO2 H CF3 tBu Cl 3119. NO2 H Cl tBu CF3 3120. NO2 H CF3 cPen Cl 3121. NO2 H Cl cPen CF3 3122. NO2 H CF3 CH2Pr Cl 3123. NO2 H Cl CH2Pr CF3 3124. NO2 H CF3 CH2CH═CH2 Cl 3125. NO2 H Cl CH2CH═CH2 CF3 3126. NO2 H CF3 CHF2 OMe 3127. NO2 H OMe CHF2 CF3 3128. NO2 H CF3 CH2CF3 Cl 3129. NO2 H Cl CH2CF3 CF3 3130. NO2 H CF3 CH2OMe Cl 3131. NO2 H Cl CH2OMe CF3 3132. NO2 H CF3 CH2CN Cl 3133. NO2 H Me Ph Me 3134. NO2 H Me Ph Cl 3135. NO2 H Et Ph Cl 3136. NO2 H Pr Ph Cl 3137. NO2 H iPr Ph Cl 3138. NO2 H CF3 Ph Cl 3139. NO2 H CF3 Ph Me 3140. NO2 H CF3 Ph CF3 3141. NO2 H CF3 Ph F 3142. NO2 H CF3 Ph OMe 3143. NO2 H CF3 Ph OEt 3144. NO2 H CF3 Ph OCHF2 3145. NO2 H CF3 Ph CN 3146. NO2 H CF3 Ph(4-Cl) Cl 3147. NO2 H Me Me OCH2CF3 3148. NO2 H CF3 Me 3149. NO2 H CF3 Me H 3150. NO2 H CF3 Me OCH2CH2OMe 3151. NO2 H CF3 Me SMe 3152. NO2 H CF3 Me OCH2CH2CH2F 3153. NO2 H CF3 Me OCH(CH2F)2 3154. NO2 H CF3 Me OCH2CF2CHF2 3155. NO2 H CF3 Me OCH2CF═CH2 3156. NO2 H CF3 Me OCH(Me)CF3 3157. NO2 H CF3 Me OCH(Me)CH2F 3158. NO2 H OCH2CF3 Me CF3 3159. NO2 H OCH2CF3 Me CHF2 3160. NO2 H CHF2 Me CHF2 3161. NO2 H CF3 Me CHF2 3162. NO2 H Cl Me OCHF2 3163. NO2 H Br Me OCHF2 3164. NO2 H Br Me CF3 3165. CHF2 H CF3 Ph Cl 3166. CHF2 H CF3 tBu Cl 3167. CHF2 H CF3 CHF2 Cl 3168. CHF2 H Cl CHF2 CF3 3169. CHF2 H CF3 Me OMe 3170. CHF2 H CF3 Me CN 3171. CHF2 H Cl Et Cl 3172. CHF2 H CHF2 Me Cl 3173. CHF2 H Me Me Me 3174. CHF2 H Me Me Cl 3175. CHF2 H Cl Me Cl 3176. CHF2 H CF3 Me Cl 3177. CHF2 H Cl Me CF3 3178. CHF2 H CF3 Me F 3179. CHF2 H OMe Me CF3 3180. CHF2 H CF3 Me OEt 3181. CHF2 H CF3 Me OCHF2 3182. CHF2 H OCHF2 Me CF3 3183. CHF2 H CF3 Me OCH2CHF2 3184. CHF2 H CF3 Me OCH2CF3 3185. CHF2 H CF3 Me OCH2CN 3186. CHF2 H CF3 Me SO2Me 3187. CHF2 H CF3 Me SEt 3188. CHF2 H CF3 Me Me 3189. CHF2 H CF3 Me Et 3190. CHF2 H CF3 Et Cl 3191. CHF2 H Cl Et CF3 3192. CHF2 H CF3 iPr Cl 3193. CHF2 H Cl iPr CF3 3194. CHF2 H CF3 tBu Cl 3195. CHF2 H Cl tBu CF3 3196. CHF2 H CF3 cPen Cl 3197. CHF2 H Cl cPen CF3 3198. CHF2 H CF3 CH2cPr Cl 3199. CHF2 H Cl CH2cPr CF3 3200. CHF2 H CF3 CH2CH═CH2 Cl 3201. CHF2 H Cl CH2CH═CH2 CF3 3202. CHF2 H CF3 CHF2 OMe 3203. CHF2 H OMe CHF2 CF3 3204. CHF2 H CF3 CH2CF3 Cl 3205. CHF2 H Cl CH2CF3 CF3 3206. CHF2 H CF3 CH2OMe Cl 3207. CHF2 H Cl CH2OMe CF3 3208. CHF2 H CF3 CH2CN Cl 3209. CHF2 H Me Ph Me 3210. CHF2 H Me Ph Cl 3211. CHF2 H Et Ph Cl 3212. CHF2 H Pr Ph Cl 3213. CHF2 H iPr Ph Cl 3214. CHF2 H CF3 Ph Cl 3215. CHF2 H CF3 Ph Me 3216. CHF2 H CF3 Ph CF3 3217. CHF2 H CF3 Ph F 3218. CHF2 H CF3 Ph OMe 3219. CHF2 H CF3 Ph OEt 3220. CHF2 H CF3 Ph OCHF2 3221. CHF2 H CF3 Ph CN 3222. CHF2 H CF3 Ph(4-Cl) Cl 3223. CHF2 H Me Me OCH2CF3 3224. CHF2 H CF3 Me 3225. CHF2 H CF3 Me H 3226. CHF2 H CF3 Me OCH2CH2OMe 3227. CHF2 H CF3 Me SMe 3228. CHF2 H CF3 Me OCH2CH2CH2F 3229. CHF2 H CF3 Me OCH(CH2F)2 3230. CHF2 H CF3 Me OCH2CF2CHF2 3231. CHF2 H CF3 Me OCH2CF═CH2 3232. CHF2 H CF3 Me OCH(Me)CF3 3233. CHF2 H CF3 Me OCH(Me)CH2F 3234. CHF2 H OCH2CF3 Me CF3 3235. CHF2 H OCH2CF3 Me CHF2 3236. CHF2 H CHF2 Me CHF2 3237. CHF2 H CF3 Me CHF2 3238. CHF2 H Cl Me OCHF2 3239. CHF2 H Br Me OCHF2 3240. CHF2 H Br Me CF3 3241. Cl Cl CF3 Ph Cl 3242. Cl Cl CF3 tBu Cl 3243. Cl Cl CF3 CHF2 Cl 3244. Cl Cl Cl CHF2 CF3 3245. Cl Cl CF3 Me OMe 3246. Cl Cl CF3 Me CN 3247. Cl Cl Cl Et Cl 3248. Cl Cl CHF2 Me Cl 3249. Cl Cl Me Me Me 3250. Cl Cl Me Me Cl 3251. Cl Cl Cl Me Cl 3252. Cl Cl CF3 Me Cl 3253. Cl Cl Cl Me CF3 3254. Cl Cl CF3 Me F 3255. Cl Cl OMe Me CF3 3256. Cl Cl CF3 Me OEt 3257. Cl Cl CF3 Me OCHF2 3258. Cl Cl OCHF2 Me CF3 3259. Cl Cl CF3 Me OCH2CHF2 3260. Cl Cl CF3 Me OCH2CF3 3261. Cl Cl CF3 Me OCH2CN 3262. Cl Cl CF3 Me SO2Me 3263. Cl Cl CF3 Me SEt 3264. Cl Cl CF3 Me Me 3265. Cl Cl CF3 Me Et 3266. Cl Cl CF3 Et Cl 3267. Cl Cl Cl Et CF3 3268. Cl Cl CF3 iPr Cl 3269. Cl Cl Cl iPr CF3 3270. Cl Cl CF3 tBu Cl 3271. Cl Cl Cl tBu CF3 3272. Cl Cl CF3 cPen Cl 3273. Cl Cl Cl cPen CF3 3274. Cl Cl CF3 CH2cPr Cl 3275. Cl Cl Cl CH2cPr CF3 3276. Cl Cl CF3 CH2CH═CH2 Cl 3277. Cl Cl Cl CH2CH═CH2 CF3 3278. Cl Cl CF3 CHF2 OMe 3279. Cl Cl OMe CHF2 CF3 3280. Cl Cl CF3 CH2CF3 Cl 3281. Cl Cl Cl CH2CF3 CF3 3282. Cl Cl CF3 CH2OMe Cl 3283. Cl Cl Cl CH2OMe CF3 3284. Cl Cl CF3 CH2CN Cl 3285. Cl Cl Me Ph Me 3286. Cl Cl Me Ph Cl 3287. Cl Cl Et Ph Cl 3288. Cl Cl Pr Ph Cl 3289. Cl Cl iPr Ph Cl 3290. Cl Cl CF3 Ph Cl 3291. Cl Cl CF3 Ph Me 3292. Cl Cl CF3 Ph CF3 3293. Cl Cl CF3 Ph F 3294. Cl Cl CF3 Ph OMe 3295. Cl Cl CF3 Ph OEt 3296. Cl Cl CF3 Ph OCHF2 3297. Cl Cl CF3 Ph CN 3298. Cl Cl CF3 Ph(4-Cl) Cl 3299. Cl Cl Me Me OCH2CF3 3300. Cl Cl CF3 Me 3301. Cl Cl CF3 Me H 3302. Cl Cl CF3 Me OCH2CH2OMe 3303. Cl Cl CF3 Me SMe 3304. Cl Cl CF3 Me OCH2CH2CH2F 3305. Cl Cl CF3 Me OCH(CH2F)2 3306. Cl Cl CF3 Me OCH2CF2CHF2 3307. Cl Cl CF3 Me OCH2CF═CH2 3308. Cl Cl CF3 Me OCH(Me)CF3 3309. Cl Cl CF3 Me OCH(Me)CH2F 3310. Cl Cl OCH2CF3 Me CF3 3311. Cl Cl OCH2CF3 Me CHF2 3312. Cl Cl CHF2 Me CHF2 3313. Cl Cl CF3 Me CHF2 3314. Cl Cl Cl Me OCHF2 3315. Cl Cl Br Me OCHF2 3316. Cl Cl Br Me CF3 3317. Me Cl CF3 Ph Cl 3318. Me Cl CF3 tBu Cl 3319. Me Cl CF3 CHF2 Cl 3320. Me Cl Cl CHF2 CF3 3321. Me Cl CF3 Me OMe 3322. Me Cl CF3 Me CN 3323. Me Cl Cl Et Cl 3324. Me Cl CHF2 Me Cl 3325. Me Cl Me Me Me 3326. Me Cl Me Me Cl 3327. Me Cl Cl Me Cl 3328. Me Cl CF3 Me Cl 3329. Me Cl Cl Me CF3 3330. Me Cl CF3 Me F 3331. Me Cl OMe Me CF3 3332. Me Cl CF3 Me OEt 3333. Me Cl CF3 Me OCHF2 3334. Me Cl OCHF2 Me CF3 3335. Me Cl CF3 Me OCH2CHF2 3336. Me Cl CF3 Me OCH2CF3 3337. Me Cl CF3 Me OCH2CN 3338. Me Cl CF3 Me SO2Me 3339. Me Cl CF3 Me SEt 3340. Me Cl CF3 Me Me 3341. Me Cl CF3 Me Et 3342. Me Cl CF3 Et Cl 3343. Me Cl Cl Et CF3 3344. Me Cl CF3 iPr Cl 3345. Me Cl Cl iPr CF3 3346. Me Cl CF3 tBu Cl 3347. Me Cl Cl tBu CF3 3348. Me Cl CF3 cPen Cl 3349. Me Cl Cl cPen CF3 3350. Me Cl CF3 CH2cPr Cl 3351. Me Cl Cl CH2cPr CF3 3352. Me Cl CF3 CH2CH═CH2 Cl 3353. Me Cl Cl CH2CH═CH2 CF3 3354. Me Cl CF3 CHF2 OMe 3355. Me Cl OMe CHF2 CF3 3356. Me Cl CF3 CH2CF3 Cl 3357. Me Cl Cl CH2CF3 CF3 3358. Me Cl CF3 CH2OMe Cl 3359. Me Cl Cl CH2OMe CF3 3360. Me Cl CF3 CH2CN Cl 3361. Me Cl Me Ph Me 3362. Me Cl Me Ph Cl 3363. Me Cl Et Ph Cl 3364. Me Cl Pr Ph Cl 3365. Me Cl iPr Ph Cl 3366. Me Cl CF3 Ph Cl 3367. Me Cl CF3 Ph Me 3368. Me Cl CF3 Ph CF3 3369. Me Cl CF3 Ph F 3370. Me Cl CF3 Ph OMe 3371. Me Cl CF3 Ph OEt 3372. Me Cl CF3 Ph OCHF2 3373. Me Cl CF3 Ph CN 3374. Me Cl CF3 Ph(4-Cl) Cl 3375. Me Cl Me Me OCH2CF3 3376. Me Cl CF3 Me 3377. Me Cl CF3 Me H 3378. Me Cl CF3 Me OCH2CH2OMe 3379. Me Cl CF3 Me SMe 3380. Me Cl CF3 Me OCH2CH2CH2F 3381. Me Cl CF3 Me OCH(CH2F)2 3382. Me Cl CF3 Me OCH2CF2CHF2 3383. Me Cl CF3 Me OCH2CF═CH2 3384. Me Cl CF3 Me OCH(Me)CF3 3385. Me Cl CF3 Me OCH(Me)CH2F 3386. Me Cl OCH2CF3 Me CF3 3387. Me Cl OCH2CF3 Me CHF2 3388. Me Cl CHF2 Me CHF2 3389. Me Cl CF3 Me CHF2 3390. Me Cl Cl Me OCHF2 3391. Me Cl Br Me OCHF2 3392. Me Cl Br Me CF3 3393. Cl Me CF3 Ph Cl 3394. Cl Me CF3 tBu Cl 3395. Cl Me CF3 CHF2 Cl 3396. Cl Me Cl CHF2 CF3 3397. Cl Me CF3 Me OMe 3398. Cl Me CF3 Me CN 3399. Cl Me Cl Et Cl 3400. Cl Me CHF2 Me Cl 3401. Cl Me Me Me Me 3402. Cl Me Me Me Cl 3403. Cl Me Cl Me Cl 3404. Cl Me CF3 Me Cl 3405. Cl Me Cl Me CF3 3406. Cl Me CF3 Me F 3407. Cl Me OMe Me CF3 3408. Cl Me CF3 Me OEt 3409. Cl Me CF3 Me OCHF2 3410. Cl Me OCHF2 Me CF3 3411. Cl Me CF3 Me OCH2CHF2 3412. Cl Me CF3 Me OCH2CF3 3413. Cl Me CF3 Me OCH2CN 3414. Cl Me CF3 Me SO2Me 3415. Cl Me CF3 Me SEt 3416. Cl Me CF3 Me Me 3417. Cl Me CF3 Me Et 3418. Cl Me CF3 Et Cl 3419. Cl Me Cl Et CF3 3420. Cl Me CF3 iPr Cl 3421. Cl Me Cl iPr CF3 3422. Cl Me CF3 tBu Cl 3423. Cl Me Cl tBu CF3 3424. Cl Me CF3 cPen Cl 3425. Cl Me Cl cPen CF3 3426. Cl Me CF3 CH2cPr Cl 3427. Cl Me Cl CH2cPr CF3 3428. Cl Me CF3 CH2CH═CH2 Cl 3429. Cl Me Cl CH2CH═CH2 CF3 3430. Cl Me CF3 CHF2 OMe 3431. Cl Me OMe CHF2 CF3 3432. Cl Me CF3 CH2CF3 Cl 3433. Cl Me Cl CH2CF3 CF3 3434. Cl Me CF3 CH2OMe Cl 3435. Cl Me Cl CH2OMe CF3 3436. Cl Me CF3 CH2CN Cl 3437. Cl Me Me Ph Me 3438. Cl Me Me Ph Cl 3439. Cl Me Et Ph Cl 3440. Cl Me Pr Ph Cl 3441. Cl Me iPr Ph Cl 3442. Cl Me CF3 Ph Cl 3443. Cl Me CF3 Ph Me 3444. Cl Me CF3 Ph CF3 3445. Cl Me CF3 Ph F 3446. Cl Me CF3 Ph OMe 3447. Cl Me CF3 Ph OEt 3448. Cl Me CF3 Ph OCHF2 3449. Cl Me CF3 Ph CN 3450. Cl Me CF3 Ph(4-Cl) Cl 3451. Cl Me Me Me OCH2CF3 3452. Cl Me CF3 Me 3453. Cl Me CF3 Me H 3454. Cl Me CF3 Me OCH2CH2OMe 3455. Cl Me CF3 Me SMe 3456. Cl Me CF3 Me OCH2CH2CH2F 3457. Cl Me CF3 Me OCH(CH2F)2 3458. Cl Me CF3 Me OCH2CF2CHF2 3459. Cl Me CF3 Me OCH2CF═CH2 3460. Cl Me CF3 Me OCH(Me)CF3 3461. Cl Me CF3 Me OCH(Me)CH2F 3462. Cl Me OCH2CF3 Me CF3 3463. Cl Me OCH2CF3 Me CHF2 3464. Cl Me CHF2 Me CHF2 3465. Cl Me CF3 Me CHF2 3466. Cl Me Cl Me OCHF2 3467. Cl Me Br Me OCHF2 3468. Cl Me Br Me CF3

TABLE 4 Compounds of the formula Ib-R (Ib-R) Ex. No. R11 R12 R6 R7 R8 3469. H H CF3 Ph Cl 3470. H H CF3 tBu Cl 3471. H H CF3 CHF2 Cl 3472. H H Cl CHF2 CF3 3473. H H CF3 Me OMe 3474. H H CF3 Me CN 3475. H H Cl Et Cl 3476. H H CHF2 Me Cl 3477. H H Me Me Me 3478. H H Me Me Cl 3479. H H Cl Me Cl 3480. H H CF3 Me Cl 3481. H H Cl Me CF3 3482. H H CF3 Me F 3483. H H OMe Me CF3 3484. H H CF3 Me OEt 3485. H H CF3 Me OCHF2 3486. H H OCHF2 Me CF3 3487. H H CF3 Me OCH2CHF2 3488. H H CF3 Me OCH2CF3 3489. H H CF3 Me OCH2CN 3490. H H CF3 Me SO2Me 3491. H H CF3 Me SEt 3492. H H CF3 Me Me 3493. H H CF3 Me Et 3494. H H CF3 Et Cl 3495. H H Cl Et CF3 3496. H H CF3 iPr Cl 3497. H H Cl iPr CF3 3498. H H CF3 tBu Cl 3499. H H Cl tBu CF3 3500. H H CF3 cPen Cl 3501. H H Cl cPen CF3 3502. H H CF3 CH2cPr Cl 3503. H H Cl CH2cPr CF3 3504. H H CF3 CH2CH═CH2 Cl 3505. H H Cl CH2CH═CH2 CF3 3506. H H CF3 CHF2 OMe 3507. H H OMe CHF2 CF3 3508. H H CF3 CH2CF3 Cl 3509. H H Cl CH2CF3 CF3 3510. H H CF3 CH2OMe Cl 3511. H H Cl CH2OMe CF3 3512. H H CF3 CH2CN Cl 3513. H H Me Ph Me 3514. H H Me Ph Cl 3515. H H Et Ph Cl 3516. H H Pr Ph Cl 3517. H H iPr Ph Cl 3518. H H CF3 Ph Cl 3519. H H CF3 Ph Me 3520. H H CF3 Ph CF3 3521. H H CF3 Ph F 3522. H H CF3 Ph OMe 3523. H H CF3 Ph OEt 3524. H H CF3 Ph OCHF2 3525. H H CF3 Ph CN 3526. H H CF3 Ph(4-Cl) Cl 3527. H H Me Me OCH2CF3 3528. H H CF3 Me 3529. H H CF3 Me H 3530. H H CF3 Me OCH2CH2OMe 3531. H H CF3 Me SMe 3532. H H CF3 Me OCH2CH2CH2F 3533. H H CF3 Me OCH(CH2F)2 3534. H H CF3 Me OCH2CF2CHF2 3535. H H CF3 Me OCH2CF═CH2 3536. H H CF3 Me OCH(Me)CF3 3537. H H CF3 Me OCH(Me)CH2F 3538. H H OCH2CF3 Me CF3 3539. H H OCH2CF3 Me CHF2 3540. H H CHF2 Me CHF2 3541. H H CF3 Me CHF2 3542. H H Cl Me OCHF2 3543. H H Br Me OCHF2 3544. H H Br Me CF3 3545. F H CF3 Ph Cl 3546. F H CF3 tBu Cl 3547. F H CF3 CHF2 Cl 3548. F H Cl CHF2 CF3 3549. F H CF3 Me OMe 3550. F H CF3 Me CN 3551. F H Cl Et Cl 3552. F H CHF2 Me Cl 3553. F H Me Me Me 3554. F H Me Me Cl 3555. F H Cl Me Cl 3556. F H CF3 Me Cl 3557. F H Cl Me CF3 3558. F H CF3 Me F 3559. F H OMe Me CF3 3560. F H CF3 Me OEt 3561. F H CF3 Me OCHF2 3562. F H OCHF2 Me CF3 3563. F H CF3 Me OCH2CHF2 3564. F H CF3 Me OCH2CF3 3565. F H CF3 Me OCH2CN 3566. F H CF3 Me SO2Me 3567. F H CF3 Me SEt 3568. F H CF3 Me Me 3569. F H CF3 Me Et 3570. F H CF3 Et Cl 3571. F H Cl Et CF3 3572. F H CF3 iPr Cl 3573. F H Cl iPr CF3 3574. F H CF3 tBu Cl 3575. F H Cl tBu CF3 3576. F H CF3 cPen Cl 3577. F H Cl cPen CF3 3578. F H CF3 CH2cPr Cl 3579. F H Cl CH2cPr CF3 3580. F H CF3 CH2CH═CH2 Cl 3581. F H Cl CH2CH═CH2 CF3 3582. F H CF3 CHF2 OMe 3583. F H OMe CHF2 CF3 3584. F H CF3 CH2CF3 Cl 3585. F H Cl CH2CF3 CF3 3586. F H CF3 CH2OMe Cl 3587. F H Cl CH2OMe CF3 3588. F H CF3 CH2CN Cl 3589. F H Me Ph Me 3590. F H Me Ph Cl 3591. F H Et Ph Cl 3592. F H Pr Ph Cl 3593. F H iPr Ph Cl 3594. F H CF3 Ph Cl 3595. F H CF3 Ph Me 3596. F H CF3 Ph CF3 3597. F H CF3 Ph F 3598. F H CF3 Ph OMe 3599. F H CF3 Ph OEt 3600. F H CF3 Ph OCHF2 3601. F H CF3 Ph CN 3602. F H CF3 Ph(4-Cl) Cl 3603. F H Me Me OCH2CF3 3604. F H CF3 Me 3605. F H CF3 Me H 3606. F H CF3 Me OCH2CH2OMe 3607. F H CF3 Me SMe 3608. F H CF3 Me OCH2CH2CH2F 3609. F H CF3 Me OCH(CH2F)2 3610. F H CF3 Me OCH2CF2CHF2 3611. F H CF3 Me OCH2CF═CH2 3612. F H CF3 Me OCH(Me)CF3 3613. F H CF3 Me OCH(Me)CH2F 3614. F H OCH2CF3 Me CF3 3615. F H OCH2CF3 Me CHF2 3616. F H CHF2 Me CHF2 3617. F H CF3 Me CHF2 3618. F H Cl Me OCHF2 3619. F H Br Me OCHF2 3620. F H Br Me CF3 3621. F H CF3 Me CF3 3622. F H CHF2 Me OCHF2 3623. F H CHF2 Me CF3 3624. F H CF2CF3 Me CF3 3625. F H CF3 Me CF2CF3 3626. F H CHF2 Me OCH2CF3 3627. Cl H CF3 Ph Cl 3628. Cl H CF3 tBu Cl 3629. Cl H CF3 CHF2 Cl 3630. Cl H Cl CHF2 CF3 3631. Cl H CF3 Me OMe 3632. Cl H CF3 Me CN 3633. Cl H Cl Et Cl 3634. Cl H CHF2 Me Cl 3635. Cl H Me Me Me 3636. Cl H Me Me Cl 3637. Cl H Cl Me Cl 3638. Cl H CF3 Me Cl 3639. Cl H Cl Me CF3 3640. Cl H CF3 Me F 3641. Cl H OMe Me CF3 3642. Cl H CF3 Me OEt 3643. Cl H CF3 Me OCHF2 3644. Cl H OCHF2 Me CF3 3645. Cl H CF3 Me OCH2CHF2 3646. Cl H CF3 Me OCH2CF3 3647. Cl H CF3 Me OCH2CN 3648. Cl H CF3 Me SO2Me 3649. Cl H CF3 Me SEt 3650. Cl H CF3 Me Me 3651. Cl H CF3 Me Et 3652. Cl H CF3 Et Cl 3653. Cl H Cl Et CF3 3654. Cl H CF3 iPr Cl 3655. Cl H Cl iPr CF3 3656. Cl H CF3 tBu Cl 3657. Cl H Cl tBu CF3 3658. Cl H CF3 cPen Cl 3659. Cl H Cl cPen CF3 3660. Cl H CF3 CH2cPr Cl 3661. Cl H Cl CH2cPr CF3 3662. Cl H CF3 CH2CH═CH2 Cl 3663. Cl H Cl CH2CH═CH2 CF3 3664. Cl H CF3 CHF2 OMe 3665. Cl H OMe CHF2 CF3 3666. Cl H CF3 CH2CF3 Cl 3667. Cl H Cl CH2CF3 CF3 3668. Cl H CF3 CH2OMe Cl 3669. Cl H Cl CH2OMe CF3 3670. Cl H CF3 CH2CN Cl 3671. Cl H Me Ph Me 3672. Cl H Me Ph Cl 3673. Cl H Et Ph Cl 3674. Cl H Pr Ph Cl 3675. Cl H iPr Ph Cl 3676. Cl H CF3 Ph Cl 3677. Cl H CF3 Ph Me 3678. Cl H CF3 Ph CF3 3679. Cl H CF3 Ph F 3680. Cl H CF3 Ph OMe 3681. Cl H CF3 Ph OEt 3682. Cl H CF3 Ph OCHF2 3683. Cl H CF3 Ph CN 3684. Cl H CF3 Ph(4-Cl) Cl 3685. Cl H Me Me OCH2CF3 3686. Cl H CF3 Me 3687. Cl H CF3 Me H 3688. Cl H CF3 Me OCH2CH2OMe 3689. Cl H CF3 Me SMe 3690. Cl H CF3 Me OCH2CH2CH2F 3691. Cl H CF3 Me OCH(CH2F)2 3692. Cl H CF3 Me OCH2CF2CHF2 3693. Cl H CF3 Me OCH2CF═CH2 3694. Cl H CF3 Me OCH(Me)CF3 3695. Cl H CF3 Me OCH(Me)CH2F 3696. Cl H OCH2CF3 Me CF3 3697. Cl H OCH2CF3 Me CHF2 3698. Cl H CHF2 Me CHF2 3699. Cl H CF3 Me CHF2 3700. Cl H Cl Me OCHF2 3701. Cl H Br Me OCHF2 3702. Cl H Br Me CF3 3703. Cl H CF3 Me CF3 3704. Cl H CHF2 Me OCHF2 3705. Cl H CHF2 Me CF3 3706. Cl H CF2CF3 Me CF3 3707. Cl H CF3 Me CF2CF3 3708. Cl H CHF2 Me OCH2CF3 3709. Br H CF3 Ph Cl 3710. Br H CF3 tBu Cl 3711. Br H CF3 CHF2 Cl 3712. Br H Cl CHF2 CF3 3713. Br H CF3 Me OMe 3714. Br H CF3 Me CN 3715. Br H Cl Et Cl 3716. Br H CHF2 Me Cl 3717. Br H Me Me Me 3718. Br H Me Me Cl 3719. Br H Cl Me Cl 3720. Br H CF3 Me Cl 3721. Br H Cl Me CF3 3722. Br H CF3 Me F 3723. Br H OMe Me CF3 3724. Br H CF3 Me OEt 3725. Br H CF3 Me OCHF2 3726. Br H OCHF2 Me CF3 3727. Br H CF3 Me OCH2CHF2 3728. Br H CF3 Me OCH2CF3 3729. Br H CF3 Me OCH2CN 3730. Br H CF3 Me SO2Me 3731. Br H CF3 Me SEt 3732. Br H CF3 Me Me 3733. Br H CF3 Me Et 3734. Br H CF3 Et Cl 3735. Br H Cl Et CF3 3736. Br H CF3 iPr Cl 3737. Br H Cl iPr CF3 3738. Br H CF3 tBu Cl 3739. Br H Cl tBu CF3 3740. Br H CF3 cPen Cl 3741. Br H Cl cPen CF3 3742. Br H CF3 CH2cPr Cl 3743. Br H Cl CH2cPr CF3 3744. Br H CF3 CH2CH═CH2 Cl 3745. Br H Cl CH2CH═CH2 CF3 3746. Br H CF3 CHF2 OMe 3747. Br H OMe CHF2 CF3 3748. Br H CF3 CH2CF3 Cl 3749. Br H Cl CH2CF3 CF3 3750. Br H CF3 CH2OMe Cl 3751. Br H Cl CH2OMe CF3 3752. Br H CF3 CH2CN Cl 3753. Br H Me Ph Me 3754. Br H Me Ph Cl 3755. Br H Et Ph Cl 3756. Br H Pr Ph Cl 3757. Br H iPr Ph Cl 3758. Br H CF3 Ph Cl 3759. Br H CF3 Ph Me 3760. Br H CF3 Ph CF3 3761. Br H CF3 Ph F 3762. Br H CF3 Ph OMe 3763. Br H CF3 Ph OEt 3764. Br H CF3 Ph OCHF2 3765. Br H CF3 Ph CN 3766. Br H CF3 Ph(4-Cl) Cl 3767. Br H Me Me OCH2CF3 3768. Br H CF3 Me 3769. Br H CF3 Me H 3770. Br H CF3 Me OCH2CH2OMe 3771. Br H CF3 Me SMe 3772. Br H CF3 Me OCH2CH2CH2F 3773. Br H CF3 Me OCH(CH2F)2 3774. Br H CF3 Me OCH2CF2CHF2 3775. Br H CF3 Me OCH2CF═CH2 3776. Br H CF3 Me OCH(Me)CF3 3777. Br H CF3 Me OCH(Me)CH2F 3778. Br H OCH2CF3 Me CF3 3779. Br H OCH2CF3 Me CHF2 3780. Br H CHF2 Me CHF2 3781. Br H CF3 Me CHF2 3782. Br H Cl Me OCHF2 3783. Br H Br Me OCHF2 3784. Br H Br Me CF3 3785. Br H CF3 Me CF3 3786. Br H CHF2 Me OCHF2 3787. Br H CHF2 Me CF3 3788. Br H CF2CF3 Me CF3 3789. Br H CF3 Me CF2CF3 3790. Br H CHF2 Me OCH2CF3 3791. I H CF3 Ph Cl 3792. I H CF3 tBu Cl 3793. I H CF3 CHF2 Cl 3794. I H Cl CHF2 CF3 3795. I H CF3 Me OMe 3796. I H CF3 Me CN 3797. I H Cl Et Cl 3798. I H CHF2 Me Cl 3799. I H Me Me Me 3800. I H Me Me Cl 3801. I H Cl Me Cl 3802. I H CF3 Me Cl 3803. I H Cl Me CF3 3804. I H CF3 Me F 3805. I H OMe Me CF3 3806. I H CF3 Me OEt 3807. I H CF3 Me OCHF2 3808. I H OCHF2 Me CF3 3809. I H CF3 Me OCH2CHF2 3810. I H CF3 Me OCH2CF3 3811. I H CF3 Me OCH2CN 3812. I H CF3 Me SO2Me 3813. I H CF3 Me SEt 3814. I H CF3 Me Me 3815. I H CF3 Me Et 3816. I H CF3 Et Cl 3817. I H Cl Et CF3 3818. I H CF3 iPr Cl 3819. I H Cl iPr CF3 3820. I H CF3 tBu Cl 3821. I H Cl tBu CF3 3822. I H CF3 cPen Cl 3823. I H Cl cPen CF3 3824. I H CF3 CH2cPr Cl 3825. I H Cl CH2cPr CF3 3826. I H CF3 CH2CH═CH2 Cl 3827. I H Cl CH2CH═CH2 CF3 3828. I H CF3 CHF2 OMe 3829. I H OMe CHF2 CF3 3830. I H CF3 CH2CF3 Cl 3831. I H Cl CH2CF3 CF3 3832. I H CF3 CH2OMe Cl 3833. I H Cl CH2OMe CF3 3834. I H CF3 CH2CN Cl 3835. I H Me Ph Me 3836. I H Me Ph Cl 3837. I H Et Ph Cl 3838. I H Pr Ph Cl 3839. I H iPr Ph Cl 3840. I H CF3 Ph Cl 3841. I H CF3 Ph Me 3842. I H CF3 Ph CF3 3843. I H CF3 Ph F 3844. I H CF3 Ph OMe 3845. I H CF3 Ph OEt 3846. I H CF3 Ph OCHF2 3847. I H CF3 Ph CN 3848. I H CF3 Ph(4-Cl) Cl 3849. I H Me Me OCH2CF3 3850. I H CF3 Me 3851. I H CF3 Me H 3852. I H CF3 Me OCH2CH2OMe 3853. I H CF3 Me SMe 3854. I H CF3 Me OCH2CH2CH2F 3855. I H CF3 Me OCH(CH2F)2 3856. I H CF3 Me OCH2CF2CHF2 3857. I H CF3 Me OCH2CF═CH2 3858. I H CF3 Me OCH(Me)CF3 3859. I H CF3 Me OCH(Me)CH2F 3860. I H OCH2CF3 Me CF3 3861. I H OCH2CF3 Me CHF2 3862. I H CHF2 Me CHF2 3863. I H CF3 Me CHF2 3864. I H Cl Me OCHF2 3865. I H Br Me OCHF2 3866. I H Br Me CF3 3867. I H CF3 Me CF3 3868. I H CHF2 Me OCHF2 3869. I H CHF2 Me CF3 3870. I H CF2CF3 Me CF3 3871. I H CF3 Me CF2CF3 3872. I H CHF2 Me OCH2CF3 3873. H Cl CF3 Ph Cl 3874. H Cl CF3 tBu Cl 3875. H Cl CF3 CHF2 Cl 3876. H Cl Cl CHF2 CF3 3877. H Cl CF3 Me OMe 3878. H Cl CF3 Me CN 3879. H Cl Cl Et Cl 3880. H Cl CHF2 Me Cl 3881. H Cl Me Me Me 3882. H Cl Me Me Cl 3883. H Cl Cl Me Cl 3884. H Cl CF3 Me Cl 3885. H Cl Cl Me CF3 3886. H Cl CF3 Me F 3887. H Cl OMe Me CF3 3888. H Cl CF3 Me OEt 3889. H Cl CF3 Me OCHF2 3890. H Cl OCHF2 Me CF3 3891. H Cl CF3 Me OCH2CHF2 3892. H Cl CF3 Me OCH2CF3 3893. H Cl CF3 Me OCH2CN 3894. H Cl CF3 Me SO2Me 3895. H Cl CF3 Me SEt 3896. H Cl CF3 Me Me 3897. H Cl CF3 Me Et 3898. H Cl CF3 Et Cl 3899. H Cl Cl Et CF3 3900. H Cl CF3 iPr Cl 3901. H Cl Cl iPr CF3 3902. H Cl CF3 tBu Cl 3903. H Cl Cl tBu CF3 3904. H Cl CF3 cPen Cl 3905. H Cl Cl cPen CF3 3906. H Cl CF3 CH2cPr Cl 3907. H Cl Cl CH2cPr CF3 3908. H Cl CF3 CH2CH═CH2 Cl 3909. H Cl Cl CH2CH═CH2 CF3 3910. H Cl CF3 CHF2 OMe 3911. H Cl OMe CHF2 CF3 3912. H Cl CF3 CH2CF3 Cl 3913. H Cl Cl CH2CF3 CF3 3914. H Cl CF3 CH2OMe Cl 3915. H Cl Cl CH2OMe CF3 3916. H Cl CF3 CH2CN Cl 3917. H Cl Me Ph Me 3918. H Cl Me Ph Cl 3919. H Cl Et Ph Cl 3920. H Cl Pr Ph Cl 3921. H Cl iPr Ph Cl 3922. H Cl CF3 Ph Cl 3923. H Cl CF3 Ph Me 3924. H Cl CF3 Ph CF3 3925. H Cl CF3 Ph F 3926. H Cl CF3 Ph OMe 3927. H Cl CF3 Ph OEt 3928. H Cl CF3 Ph OCHF2 3929. H Cl CF3 Ph CN 3930. H Cl CF3 Ph(4-Cl) Cl 3931. H Cl Me Me OCH2CF3 3932. H Cl CF3 Me 3933. H Cl CF3 Me H 3934. H Cl CF3 Me OCH2CH2OMe 3935. H Cl CF3 Me SMe 3936. H Cl CF3 Me OCH2CH2CH2F 3937. H Cl CF3 Me OCH(CH2F)2 3938. H Cl CF3 Me OCH2CF2CHF2 3939. H Cl CF3 Me OCH2CF═CH2 3940. H Cl CF3 Me OCH(Me)CF3 3941. H Cl CF3 Me OCH(Me)CH2F 3942. H Cl OCH2CF3 Me CF3 3943. H Cl OCH2CF3 Me CHF2 3944. H Cl CHF2 Me CHF2 3945. H Cl CF3 Me CHF2 3946. H Cl Cl Me OCHF2 3947. H Cl Br Me OCHF2 3948. H Cl Br Me CF3 3949. H Br CF3 Ph Cl 3950. H Br CF3 tBu Cl 3951. H Br CF3 CHF2 Cl 3952. H Br Cl CHF2 CF3 3953. H Br CF3 Me OMe 3954. H Br CF3 Me CN 3955. H Br Cl Et Cl 3956. H Br CHF2 Me Cl 3957. H Br Me Me Me 3958. H Br Me Me Cl 3959. H Br Cl Me Cl 3960. H Br CF3 Me Cl 3961. H Br Cl Me CF3 3962. H Br CF3 Me F 3963. H Br OMe Me CF3 3964. H Br CF3 Me OEt 3965. H Br CF3 Me OCHF2 3966. H Br OCHF2 Me CF3 3967. H Br CF3 Me OCH2CHF2 3968. H Br CF3 Me OCH2CF3 3969. H Br CF3 Me OCH2CN 3970. H Br CF3 Me SO2Me 3971. H Br CF3 Me SEt 3972. H Br CF3 Me Me 3973. H Br CF3 Me Et 3974. H Br CF3 Et Cl 3975. H Br Cl Et CF3 3976. H Br CF3 iPr Cl 3977. H Br Cl iPr CF3 3978. H Br CF3 tBu Cl 3979. H Br Cl tBu CF3 3980. H Br CF3 cPen Cl 3981. H Br Cl cPen CF3 3982. H Br CF3 CH2cPr Cl 3983. H Br Cl CH2cPr CF3 3984. H Br CF3 CH2CH═CH2 Cl 3985. H Br Cl CH2CH═CH2 CF3 3986. H Br CF3 CHF2 OMe 3987. H Br OMe CHF2 CF3 3988. H Br CF3 CH2CF3 Cl 3989. H Br Cl CH2CF3 CF3 3990. H Br CF3 CH2OMe Cl 3991. H Br Cl CH2OMe CF3 3992. H Br CF3 CH2CN Cl 3993. H Br Me Ph Me 3994. H Br Me Ph Cl 3995. H Br Et Ph Cl 3996. H Br Pr Ph Cl 3997. H Br iPr Ph Cl 3998. H Br CF3 Ph Cl 3999. H Br CF3 Ph Me 4000. H Br CF3 Ph CF3 4001. H Br CF3 Ph F 4002. H Br CF3 Ph OMe 4003. H Br CF3 Ph OEt 4004. H Br CF3 Ph OCHF2 4005. H Br CF3 Ph CN 4006. H Br CF3 Ph(4-Cl) Cl 4007. H Br Me Me OCH2CF3 4008. H Br CF3 Me 4009. H Br CF3 Me H 4010. H Br CF3 Me OCH2CH2OMe 4011. H Br CF3 Me SMe 4012. H Br CF3 Me OCH2CH2CH2F 4013. H Br CF3 Me OCH(CH2F)2 4014. H Br CF3 Me OCH2CF2CHF2 4015. H Br CF3 Me OCH2CF═CH2 4016. H Br CF3 Me OCH(Me)CF3 4017. H Br CF3 Me OCH(Me)CH2F 4018. H Br OCH2CF3 Me CF3 4019. H Br OCH2CF3 Me CHF2 4020. H Br CHF2 Me CHF2 4021. H Br CF3 Me CHF2 4022. H Br Cl Me OCHF2 4023. H Br Br Me OCHF2 4024. H Br Br Me CF3 4025. Me H CF3 Ph Cl 4026. Me H CF3 tBu Cl 4027. Me H CF3 CHF2 Cl 4028. Me H Cl CHF2 CF3 4029. Me H CF3 Me OMe 4030. Me H CF3 Me CN 4031. Me H Cl Et Cl 4032. Me H CHF2 Me Cl 4033. Me H Me Me Me 4034. Me H Me Me Cl 4035. Me H Cl Me Cl 4036. Me H CF3 Me Cl 4037. Me H Cl Me CF3 4038. Me H CF3 Me F 4039. Me H OMe Me CF3 4040. Me H CF3 Me OEt 4041. Me H CF3 Me OCHF2 4042. Me H OCHF2 Me CF3 4043. Me H CF3 Me OCH2CHF2 4044. Me H CF3 Me OCH2CF3 4045. Me H CF3 Me OCH2CN 4046. Me H CF3 Me SO2Me 4047. Me H CF3 Me SEt 4048. Me H CF3 Me Me 4049. Me H CF3 Me Et 4050. Me H CF3 Et Cl 4051. Me H Cl Et CF3 4052. Me H CF3 iPr Cl 4053. Me H Cl iPr CF3 4054. Me H CF3 tBu Cl 4055. Me H Cl tBu CF3 4056. Me H CF3 cPen Cl 4057. Me H Cl cPen CF3 4058. Me H CF3 CH2cPr Cl 4059. Me H Cl CH2cPr CF3 4060. Me H CF3 CH2CH═CH2 Cl 4061. Me H Cl CH2CH═CH2 CF3 4062. Me H CF3 CHF2 OMe 4063. Me H OMe CHF2 CF3 4064. Me H CF3 CH2CF3 Cl 4065. Me H Cl CH2CF3 CF3 4066. Me H CF3 CH2OMe Cl 4067. Me H Cl CH2OMe CF3 4068. Me H CF3 CH2CN Cl 4069. Me H Me Ph Me 4070. Me H Me Ph Cl 4071. Me H Et Ph Cl 4072. Me H Pr Ph Cl 4073. Me H iPr Ph Cl 4074. Me H CF3 Ph Cl 4075. Me H CF3 Ph Me 4076. Me H CF3 Ph CF3 4077. Me H CF3 Ph F 4078. Me H CF3 Ph OMe 4079. Me H CF3 Ph OEt 4080. Me H CF3 Ph OCHF2 4081. Me H CF3 Ph CN 4082. Me H CF3 Ph(4-Cl) Cl 4083. Me H Me Me OCH2CF3 4084. Me H CF3 Me 4085. Me H CF3 Me H 4086. Me H CF3 Me OCH2CH2OMe 4087. Me H CF3 Me SMe 4088. Me H CF3 Me OCH2CH2CH2F 4089. Me H CF3 Me OCH(CH2F)2 4090. Me H CF3 Me OCH2CF2CHF2 4091. Me H CF3 Me OCH2CF═CH2 4092. Me H CF3 Me OCH(Me)CF3 4093. Me H CF3 Me OCH(Me)CH2F 4094. Me H OCH2CF3 Me CF3 4095. Me H OCH2CF3 Me CHF2 4096. Me H CHF2 Me CHF2 4097. Me H CF3 Me CHF2 4098. Me H Cl Me OCHF2 4099. Me H Br Me OCHF2 4100. Me H Br Me CF3 4101. H Me CF3 Ph Cl 4102. H Me CF3 tBu Cl 4103. H Me CF3 CHF2 Cl 4104. H Me Cl CHF2 CF3 4105. H Me CF3 Me OMe 4106. H Me CF3 Me CN 4107. H Me Cl Et Cl 4108. H Me CHF2 Me Cl 4109. H Me Me Me Me 4110. H Me Me Me Cl 4111. H Me Cl Me Cl 4112. H Me CF3 Me Cl 4113. H Me Cl Me CF3 4114. H Me CF3 Me F 4115. H Me OMe Me CF3 4116. H Me CF3 Me OEt 4117. H Me CF3 Me OCHF2 4118. H Me OCHF2 Me CF3 4119. H Me CF3 Me OCH2CHF2 4120. H Me CF3 Me OCH2CF3 4121. H Me CF3 Me OCH2CN 4122. H Me CF3 Me SO2Me 4123. H Me CF3 Me SEt 4124. H Me CF3 Me Me 4125. H Me CF3 Me Et 4126. H Me CF3 Et Cl 4127. H Me Cl Et CF3 4128. H Me CF3 iPr Cl 4129. H Me Cl iPr CF3 4130. H Me CF3 tBu Cl 4131. H Me Cl tBu CF3 4132. H Me CF3 cPen Cl 4133. H Me Cl cPen CF3 4134. H Me CF3 CH2cPr Cl 4135. H Me Cl CH2cPr CF3 4136. H Me CF3 CH2CH═CH2 Cl 4137. H Me Cl CH2CH═CH2 CF3 4138. H Me CF3 CHF2 OMe 4139. H Me OMe CHF2 CF3 4140. H Me CF3 CH2CF3 Cl 4141. H Me Cl CH2CF3 CF3 4142. H Me CF3 CH2OMe Cl 4143. H Me Cl CH2OMe CF3 4144. H Me CF3 CH2CN Cl 4145. H Me Me Ph Me 4146. H Me Me Ph Cl 4147. H Me Et Ph Cl 4148. H Me Pr Ph Cl 4149. H Me iPr Ph Cl 4150. H Me CF3 Ph Cl 4151. H Me CF3 Ph Me 4152. H Me CF3 Ph CF3 4153. H Me CF3 Ph F 4154. H Me CF3 Ph OMe 4155. H Me CF3 Ph OEt 4156. H Me CF3 Ph OCHF2 4157. H Me CF3 Ph CN 4158. H Me CF3 Ph(4-Cl) Cl 4159. H Me Me Me OCH2CF3 4160. H Me CF3 Me 4161. H Me CF3 Me H 4162. H Me CF3 Me OCH2CH2OMe 4163. H Me CF3 Me SMe 4164. H Me CF3 Me OCH2CH2CH2F 4165. H Me CF3 Me OCH(CH2F)2 4166. H Me CF3 Me OCH2CF2CHF2 4167. H Me CF3 Me OCH2CF═CH2 4168. H Me CF3 Me OCH(Me)CF3 4169. H Me CF3 Me OCH(Me)CH2F 4170. H Me OCH2CF3 Me CF3 4171. H Me OCH2CF3 Me CHF2 4172. H Me CHF2 Me CHF2 4173. H Me CF3 Me CHF2 4174. H Me Cl Me OCHF2 4175. H Me Br Me OCHF2 4176. H Me Br Me CF3 4177. NO2 H CF3 Ph Cl 4178. NO2 H CF3 tBu Cl 4179. NO2 H CF3 CHF2 Cl 4180. NO2 H Cl CHF2 CF3 4181. NO2 H CF3 Me OMe 4182. NO2 H CF3 Me CN 4183. NO2 H Cl Et Cl 4184. NO2 H CHF2 Me Cl 4185. NO2 H Me Me Me 4186. NO2 H Me Me Cl 4187. NO2 H Cl Me Cl 4188. NO2 H CF3 Me Cl 4189. NO2 H Cl Me CF3 4190. NO2 H CF3 Me F 4191. NO2 H OMe Me CF3 4192. NO2 H CF3 Me OEt 4193. NO2 H CF3 Me OCHF2 4194. NO2 H OCHF2 Me CF3 4195. NO2 H CF3 Me OCH2CHF2 4196. NO2 H CF3 Me OCH2CF3 4197. NO2 H CF3 Me OCH2CN 4198. NO2 H CF3 Me SO2Me 4199. NO2 H CF3 Me SEt 4200. NO2 H CF3 Me Me 4201. NO2 H CF3 Me Et 4202. NO2 H CF3 Et Cl 4203. NO2 H Cl Et CF3 4204. NO2 H CF3 iPr Cl 4205. NO2 H Cl iPr CF3 4206. NO2 H CF3 tBu Cl 4207. NO2 H Cl tBu CF3 4208. NO2 H CF3 cPen Cl 4209. NO2 H Cl cPen CF3 4210. NO2 H CF3 CH2cPr Cl 4211. NO2 H Cl CH2cPr CF3 4212. NO2 H CF3 CH2CH═CH2 Cl 4213. NO2 H Cl CH2CH═CH2 CF3 4214. NO2 H CF3 CHF2 OMe 4215. NO2 H OMe CHF2 CF3 4216. NO2 H CF3 CH2CF3 Cl 4217. NO2 H Cl CH2CF3 CF3 4218. NO2 H CF3 CH2OMe Cl 4219. NO2 H Cl CH2OMe CF3 4220. NO2 H CF3 CH2CN Cl 4221. NO2 H Me Ph Me 4222. NO2 H Me Ph Cl 4223. NO2 H Et Ph Cl 4224. NO2 H Pr Ph Cl 4225. NO2 H iPr Ph Cl 4226. NO2 H CF3 Ph Cl 4227. NO2 H CF3 Ph Me 4228. NO2 H CF3 Ph CF3 4229. NO2 H CF3 Ph F 4230. NO2 H CF3 Ph OMe 4231. NO2 H CF3 Ph OEt 4232. NO2 H CF3 Ph OCHF2 4233. NO2 H CF3 Ph CN 4234. NO2 H CF3 Ph(4-Cl) Cl 4235. NO2 H Me Me OCH2CF3 4236. NO2 H CF3 Me 4237. NO2 H CF3 Me H 4238. NO2 H CF3 Me OCH2CH2OMe 4239. NO2 H CF3 Me SMe 4240. NO2 H CF3 Me OCH2CH2CH2F 4241. NO2 H CF3 Me OCH(CH2F)2 4242. NO2 H CF3 Me OCH2CF2CHF2 4243. NO2 H CF3 Me OCH2CF═CH2 4244. NO2 H CF3 Me OCH(Me)CF3 4245. NO2 H CF3 Me OCH(Me)CH2F 4246. NO2 H OCH2CF3 Me CF3 4247. NO2 H OCH2CF3 Me CHF2 4248. NO2 H CHF2 Me CHF2 4249. NO2 H CF3 Me CHF2 4250. NO2 H Cl Me OCHF2 4251. NO2 H Br Me OCHF2 4252. NO2 H Br Me CF3 4253. CHF2 H CF3 Ph Cl 4254. CHF2 H CF3 tBu Cl 4255. CHF2 H CF3 CHF2 Cl 4256. CHF2 H Cl CHF2 CF3 4257. CHF2 H CF3 Me OMe 4258. CHF2 H CF3 Me CN 4259. CHF2 H Cl Et Cl 4260. CHF2 H CHF2 Me Cl 4261. CHF2 H Me Me Me 4262. CHF2 H Me Me Cl 4263. CHF2 H Cl Me Cl 4264. CHF2 H CF3 Me Cl 4265. CHF2 H Cl Me CF3 4266. CHF2 H CF3 Me F 4267. CHF2 H OMe Me CF3 4268. CHF2 H CF3 Me OEt 4269. CHF2 H CF3 Me OCHF2 4270. CHF2 H OCHF2 Me CF3 4271. CHF2 H CF3 Me OCH2CHF2 4272. CHF2 H CF3 Me OCH2CF3 4273. CHF2 H CF3 Me OCH2CN 4274. CHF2 H CF3 Me SO2Me 4275. CHF2 H CF3 Me SEt 4276. CHF2 H CF3 Me Me 4277. CHF2 H CF3 Me Et 4278. CHF2 H CF3 Et Cl 4279. CHF2 H Cl Et CF3 4280. CHF2 H CF3 iPr Cl 4281. CHF2 H Cl iPr CF3 4282. CHF2 H CF3 tBu Cl 4283. CHF2 H Cl tBu CF3 4284. CHF2 H CF3 cPen Cl 4285. CHF2 H Cl cPen CF3 4286. CHF2 H CF3 CH2cPr Cl 4287. CHF2 H Cl CH2cPr CF3 4288. CHF2 H CF3 CH2CH═CH2 Cl 4289. CHF2 H Cl CH2CH═CH2 CF3 4290. CHF2 H CF3 CHF2 OMe 4291. CHF2 H OMe CHF2 CF3 4292. CHF2 H CF3 CH2CF3 Cl 4293. CHF2 H Cl CH2CF3 CF3 4294. CHF2 H CF3 CH2OMe Cl 4295. CHF2 H Cl CH2OMe CF3 4296. CHF2 H CF3 CH2CN Cl 4297. CHF2 H Me Ph Me 4298. CHF2 H Me Ph Cl 4299. CHF2 H Et Ph Cl 4300. CHF2 H Pr Ph Cl 4301. CHF2 H iPr Ph Cl 4302. CHF2 H CF3 Ph Cl 4303. CHF2 H CF3 Ph Me 4304. CHF2 H CF3 Ph CF3 4305. CHF2 H CF3 Ph F 4306. CHF2 H CF3 Ph OMe 4307. CHF2 H CF3 Ph OEt 4308. CHF2 H CF3 Ph OCHF2 4309. CHF2 H CF3 Ph CN 4310. CHF2 H CF3 Ph(4-Cl) Cl 4311. CHF2 H Me Me OCH2CF3 4312. CHF2 H CF3 Me 4313. CHF2 H CF3 Me H 4314. CHF2 H CF3 Me OCH2CH2OMe 4315. CHF2 H CF3 Me SMe 4316. CHF2 H CF3 Me OCH2CH2CH2F 4317. CHF2 H CF3 Me OCH(CH2F)2 4318. CHF2 H CF3 Me OCH2CF2CHF2 4319. CHF2 H CF3 Me OCH2CF═CH2 4320. CHF2 H CF3 Me OCH(Me)CF3 4321. CHF2 H CF3 Me OCH(Me)CH2F 4322. CHF2 H OCH2CF3 Me CF3 4323. CHF2 H OCH2CF3 Me CHF2 4324. CHF2 H CHF2 Me CHF2 4325. CHF2 H CF3 Me CHF2 4326. CHF2 H Cl Me OCHF2 4327. CHF2 H Br Me OCHF2 4328. CHF2 H Br Me CF3 4329. Cl Cl CF3 Ph Cl 4330. Cl Cl CF3 tBu Cl 4331. Cl Cl CF3 CHF2 Cl 4332. Cl Cl Cl CHF2 CF3 4333. Cl Cl CF3 Me OMe 4334. Cl Cl CF3 Me CN 4335. Cl Cl Cl Et Cl 4336. Cl Cl CHF2 Me Cl 4337. Cl Cl Me Me Me 4338. Cl Cl Me Me Cl 4339. Cl Cl Cl Me Cl 4340. Cl Cl CF3 Me Cl 4341. Cl Cl Cl Me CF3 4342. Cl Cl CF3 Me F 4343. Cl Cl OMe Me CF3 4344. Cl Cl CF3 Me OEt 4345. Cl Cl CF3 Me OCHF2 4346. Cl Cl OCHF2 Me CF3 4347. Cl Cl CF3 Me OCH2CHF2 4348. Cl Cl CF3 Me OCH2CF3 4349. Cl Cl CF3 Me OCH2CN 4350. Cl Cl CF3 Me SO2Me 4351. Cl Cl CF3 Me SEt 4352. Cl Cl CF3 Me Me 4353. Cl Cl CF3 Me Et 4354. Cl Cl CF3 Et Cl 4355. Cl Cl Cl Et CF3 4356. Cl Cl CF3 iPr Cl 4357. Cl Cl Cl iPr CF3 4358. Cl Cl CF3 tBu Cl 4359. Cl Cl Cl tBu CF3 4360. Cl Cl CF3 cPen Cl 4361. Cl Cl Cl cPen CF3 4362. Cl Cl CF3 CH2cPr Cl 4363. Cl Cl Cl CH2cPr CF3 4364. Cl Cl CF3 CH2CH═CH2 Cl 4365. Cl Cl Cl CH2CH═CH2 CF3 4366. Cl Cl CF3 CHF2 OMe 4367. Cl Cl OMe CHF2 CF3 4368. Cl Cl CF3 CH2CF3 Cl 4369. Cl Cl Cl CH2CF3 CF3 4370. Cl Cl CF3 CH2OMe Cl 4371. Cl Cl Cl CH2OMe CF3 4372. Cl Cl CF3 CH2CN Cl 4373. Cl Cl Me Ph Me 4374. Cl Cl Me Ph Cl 4375. Cl Cl Et Ph Cl 4376. Cl Cl Pr Ph Cl 4377. Cl Cl iPr Ph Cl 4378. Cl Cl CF3 Ph Cl 4379. Cl Cl CF3 Ph Me 4380. Cl Cl CF3 Ph CF3 4381. Cl Cl CF3 Ph F 4382. Cl Cl CF3 Ph OMe 4383. Cl Cl CF3 Ph OEt 4384. Cl Cl CF3 Ph OCHF2 4385. Cl Cl CF3 Ph CN 4386. Cl Cl CF3 Ph(4-Cl) Cl 4387. Cl Cl Me Me OCH2CF3 4388. Cl Cl CF3 Me 4389. Cl Cl CF3 Me H 4390. Cl Cl CF3 Me OCH2CH2OMe 4391. Cl Cl CF3 Me SMe 4392. Cl Cl CF3 Me OCH2CH2CH2F 4393. Cl Cl CF3 Me OCH(CH2F)2 4394. Cl Cl CF3 Me OCH2CF2CHF2 4395. Cl Cl CF3 Me OCH2CF═CH2 4396. Cl Cl CF3 Me OCH(Me)CF3 4397. Cl Cl CF3 Me OCH(Me)CH2F 4398. Cl Cl OCH2CF3 Me CF3 4399. Cl Cl OCH2CF3 Me CHF2 4400. Cl Cl CHF2 Me CHF2 4401. Cl Cl CF3 Me CHF2 4402. Cl Cl Cl Me OCHF2 4403. Cl Cl Br Me OCHF2 4404. Cl Cl Br Me CF3 4405. Me Cl CF3 Ph Cl 4406. Me Cl CF3 tBu Cl 4407. Me Cl CF3 CHF2 Cl 4408. Me Cl Cl CHF2 CF3 4409. Me Cl CF3 Me OMe 4410. Me Cl CF3 Me CN 4411. Me Cl Cl Et Cl 4412. Me Cl CHF2 Me Cl 4413. Me Cl Me Me Me 4414. Me Cl Me Me Cl 4415. Me Cl Cl Me Cl 4416. Me Cl CF3 Me Cl 4417. Me Cl Cl Me CF3 4418. Me Cl CF3 Me F 4419. Me Cl OMe Me CF3 4420. Me Cl CF3 Me OEt 4421. Me Cl CF3 Me OCHF2 4422. Me Cl OCHF2 Me CF3 4423. Me Cl CF3 Me OCH2CHF2 4424. Me Cl CF3 Me OCH2CF3 4425. Me Cl CF3 Me OCH2CN 4426. Me Cl CF3 Me SO2Me 4427. Me Cl CF3 Me SEt 4428. Me Cl CF3 Me Me 4429. Me Cl CF3 Me Et 4430. Me Cl CF3 Et Cl 4431. Me Cl Cl Et CF3 4432. Me Cl CF3 iPr Cl 4433. Me Cl Cl iPr CF3 4434. Me Cl CF3 tBu Cl 4435. Me Cl Cl tBu CF3 4436. Me Cl CF3 cPen Cl 4437. Me Cl Cl cPen CF3 4438. Me Cl CF3 CH2cPr Cl 4439. Me Cl Cl CH2cPr CF3 4440. Me Cl CF3 CH2CH═CH2 Cl 4441. Me Cl Cl CH2CH═CH2 CF3 4442. Me Cl CF3 CHF2 OMe 4443. Me Cl OMe CHF2 CF3 4444. Me Cl CF3 CH2CF3 Cl 4445. Me Cl Cl CH2CF3 CF3 4446. Me Cl CF3 CH2OMe Cl 4447. Me Cl Cl CH2OMe CF3 4448. Me Cl CF3 CH2CN Cl 4449. Me Cl Me Ph Me 4450. Me Cl Me Ph Cl 4451. Me Cl Et Ph Cl 4452. Me Cl Pr Ph Cl 4453. Me Cl iPr Ph Cl 4454. Me Cl CF3 Ph Cl 4455. Me Cl CF3 Ph Me 4456. Me Cl CF3 Ph CF3 4457. Me Cl CF3 Ph F 4458. Me Cl CF3 Ph OMe 4459. Me Cl CF3 Ph OEt 4460. Me Cl CF3 Ph OCHF2 4461. Me Cl CF3 Ph CN 4462. Me Cl CF3 Ph(4-Cl) Cl 4463. Me Cl Me Me OCH2CF3 4464. Me Cl CF3 Me 4465. Me Cl CF3 Me H 4466. Me Cl CF3 Me OCH2CH2OMe 4467. Me Cl CF3 Me SMe 4468. Me Cl CF3 Me OCH2CH2CH2F 4469. Me Cl CF3 Me OCH(CH2F)2 4470. Me Cl CF3 Me OCH2CF2CHF2 4471. Me Cl CF3 Me OCH2CF═CH2 4472. Me Cl CF3 Me OCH(Me)CF3 4473. Me Cl CF3 Me OCH(Me)CH2F 4474. Me Cl OCH2CF3 Me CF3 4475. Me Cl OCH2CF3 Me CHF2 4476. Me Cl CHF2 Me CHF2 4477. Me Cl CF3 Me CHF2 4478. Me Cl Cl Me OCHF2 4479. Me Cl Br Me OCHF2 4480. Me Cl Br Me CF3 4481. Cl Me CF3 Ph Cl 4482. Cl Me CF3 tBu Cl 4483. Cl Me CF3 CHF2 Cl 4484. Cl Me Cl CHF2 CF3 4485. Cl Me CF3 Me OMe 4486. Cl Me CF3 Me CN 4487. Cl Me Cl Et Cl 4488. Cl Me CHF2 Me Cl 4489. Cl Me Me Me Me 4490. Cl Me Me Me Cl 4491. Cl Me Cl Me Cl 4492. Cl Me CF3 Me Cl 4493. Cl Me Cl Me CF3 4494. Cl Me CF3 Me F 4495. Cl Me OMe Me CF3 4496. Cl Me CF3 Me OEt 4497. Cl Me CF3 Me OCHF2 4498. Cl Me OCHF2 Me CF3 4499. Cl Me CF3 Me OCH2CHF2 4500. Cl Me CF3 Me OCH2CF3 4501. Cl Me CF3 Me OCH2CN 4502. Cl Me CF3 Me SO2Me 4503. Cl Me CF3 Me SEt 4504. Cl Me CF3 Me Me 4505. Cl Me CF3 Me Et 4506. Cl Me CF3 Et Cl 4507. Cl Me Cl Et CF3 4508. Cl Me CF3 iPr Cl 4509. Cl Me Cl iPr CF3 4510. Cl Me CF3 tBu Cl 4511. Cl Me Cl tBu CF3 4512. Cl Me CF3 cPen Cl 4513. Cl Me Cl cPen CF3 4514. Cl Me CF3 CH2cPr Cl 4515. Cl Me Cl CH2cPr CF3 4516. Cl Me CF3 CH2CH═CH2 Cl 4517. Cl Me Cl CH2CH═CH2 CF3 4518. Cl Me CF3 CHF2 OMe 4519. Cl Me OMe CHF2 CF3 4520. Cl Me CF3 CH2CF3 Cl 4521. Cl Me Cl CH2CF3 CF3 4522. Cl Me CF3 CH2OMe Cl 4523. Cl Me Cl CH2OMe CF3 4524. Cl Me CF3 CH2CN Cl 4525. Cl Me Me Ph Me 4526. Cl Me Me Ph Cl 4527. Cl Me Et Ph Cl 4528. Cl Me Pr Ph Cl 4529. Cl Me iPr Ph Cl 4530. Cl Me CF3 Ph Cl 4531. Cl Me CF3 Ph Me 4532. Cl Me CF3 Ph CF3 4533. Cl Me CF3 Ph F 4534. Cl Me CF3 Ph OMe 4535. Cl Me CF3 Ph OEt 4536. Cl Me CF3 Ph OCHF2 4537. Cl Me CF3 Ph CN 4538. Cl Me CF3 Ph(4-Cl) Cl 4539. Cl Me Me Me OCH2CF3 4540. Cl Me CF3 Me 4541. Cl Me CF3 Me H 4542. Cl Me CF3 Me OCH2CH2OMe 4543. Cl Me CF3 Me SMe 4544. Cl Me CF3 Me OCH2CH2CH2F 4545. Cl Me CF3 Me OCH(CH2F)2 4546. Cl Me CF3 Me OCH2CF2CHF2 4547. Cl Me CF3 Me OCH2CF═CH2 4548. Cl Me CF3 Me OCH(Me)CF3 4549. Cl Me CF3 Me OCH(Me)CH2F 4550. Cl Me OCH2CF3 Me CF3 4551. Cl Me OCH2CF3 Me CHF2 4552. Cl Me CHF2 Me CHF2 4553. Cl Me CF3 Me CHF2 4554. Cl Me Cl Me OCHF2 4555. Cl Me Br Me OCHF2 4556. Cl Me Br Me CF3

In the tables below, retention times (Rt, in minutes) of selected compounds of Tables 1-4 of chiral compounds were measured on chiral HPLC [Chiralcel® OD column (250×4.6 mm), temperature 25° C., flow rate 0.6 ml/min, mobile phase hexane/2-propanol 90:10].

TABLE 5 Compounds of the formula Ia-S (Ia-S) Ex. Optical No. R11 R12 R1 R2 R3 R4 R5 rotation Physical data 185 Cl H Cl H H H Cl  *Rt = 20.123 min 259 Br H F H H H F  Rt = 17.053 min 270 Br H Cl H H H Cl [α]D = +160° **Rt = 26.474 min *hexane/2-propanol 95:5 v/v. **hexane/2-propanol 97:3 v/v.

TABLE 6 Compounds of the formula Ia-R (Ia-R) Ex. Optical No. R11 R12 R1 R2 R3 R4 R5 rotation Physical data 1375 Cl H Cl H H H Cl  *Rt = 22.213 min 1449 Br H F H H H F  Rt = 19.430 min 1460 Br H Cl H H H Cl [α]D = −123° **Rt = 29.369 min *hexane/2-propanol 95:5 v/v. **hexane/2-propanol 97:3 v/v.

TABLE 7 Compounds of Tables 5 and 6 of the formula (Ia) (racemates) (Ia) Ex. No. R11 R12 R1 R2 R3 R4 R5 185/1375 Cl H Cl H H H Cl 259/1449 Br H F H H H F 270/1460 Br H Cl H H H Cl

NMR Data of the compounds of Tables 5+6 (CDCl3, 400 MHz, δ in ppm):

NMR Compound 185/1375 (CDCl3, 400 MHz):

  • 4.74 (d, 1H, S(O)CH2); 4.83 (d, 1H, S(O)CH2); 7.23 (m, 1H, Ar); 7.33 (m, 2H, Ar); 7.67 (s, 1H, thiazolyl-H).

NMR Compound 259/1449 (CDCl3, 400 MHz):

  • 4.43 (d, 1H, S(O)CH2); 4.52 (d, 1H, S(O)CH2); 6.91 (m, 2H, Ar); 7.32 (m, 1H, Ar); 7.79 (s, 1H, thiazolyl-H).

NMR Compound 270/1460 (CDCl3, 400 MHz):

  • 4.74 (d, 1H, S(O)CH2); 4.83 (d, 1H, S(O)CH2); 7.24 (m, 1H, Ar); 7.34 (m, 2H, Ar); 7.77 (s, 1H, thiazolyl-H).

TABLE 8 Compounds of the formula Ib-S (Ib-S) Ex. Optical No. R11 R12 R6 R7 R8 rotation Physical data 2555 Cl H CF3 Me OCHF2 [α]D =   Rt = 10.081 min −69.6° 2632 Br H CF3 Me Cl [α]D =   Rt = 18.600 min −38.4° 2637 Br H CF3 Me OCHF2 [α]D =  [α]D = −66.6° −66.6°   Rt = 10.258 min 2719 I H CF3 Me OCHF2 [α]D =   Rt = 12.775 min −59.8° 2640 Br H CF3 Me OCH2CF3 [α]D = ***Rt = 17.973 min −36.2° ***Column Chiralpak IC, Heptane 2-Propanol 90:10, 0.6 ml/min, 25° C.

TABLE 9 Compounds of the formula Ib-R (Ib-R) Ex. Optical No. R11 R12 R6 R7 R8 rotation Physical data 3643 Cl H CF3 Me OCHF2 [α]D =   Rt = 12.219 min +71.0° 3720 Br H CF3 Me Cl [α]D =   Rt = 22.652 min +40.3° 3725 Br H CF3 Me OCHF2 [α]D =  [α]D = +78.3° +78.3°   Rt = 12.557 min 3807 I H CF3 Me OCHF2 [α]D =   Rt = 15.893 min +56.1° 3728 Br H CF3 Me OCH2CF3 [α]D = ***Rt = 16.446 min +68.4° ***Column Chiralpak IC, Heptane 2-Propanol 90:10, 0.6 ml/min, 25° C.

TABLE 10 Compounds of the formula (Ib) (racemates) (Ib) Ex. No. R11 R12 R6 R7 R8 2555/3643 Cl H CF3 Me OCHF2 2632/3720 Br H CF3 Me Cl 2637/3725 Br H CF3 Me OCHF2 2719/3807 I H CF3 Me OCHF2 2640/3728 Br H CF3 Me OCH2CF3

NMR Data of the compounds of Tables 8+9 (CDCl3, 400 MHz, δ in ppm):

NMR Compound 2555/3643 (CDCl3, 400 MHz):

  • 3.86 (s, 3H, NCH3); 4.11 (d, 1H, S(O)CH2); 4.37 (d, 1H, S(O)CH2); 6.93 (dd, 1H, OCHF2); 7.78 (s, 1H, thiazolyl-H).

NMR Compound 2632/3720 (CDCl3, 400 MHz):

  • 3.90 (s, 3H, NCH3); 4.26 (d, 1H, S(O)CH2); 4.35 (d, 1H, S(O)CH2); 7.81 (s, 1H, thiazolyl-H).

NMR Compound 2637/3725 (CDCl3, 400 MHz):

  • 3.85 (s, 3H, NCH3); 4.11 (d, 1H, S(O)CH2); 4.37 (d, 1H, S(O)CH2); 6.94 (dd, 1H, OCHF2); 7.87 (s, 1H, thiazolyl-H).

NMR Compound 2719/3807 (CDCl3, 400 MHz):

  • 3.86 (s, 3H, NCH3); 4.10 (d, 1H, S(O)CH2); 4.36 (d, 1H, S(O)CH2); 6.96 (dd, 1H, OCHF2); 7.99 (s, 1H, thiazolyl-H).

NMR Compound 2640/3728 (CDCl3, 400 MHz):

  • 3.81 (s, 3H, NCH3); 4.10 (d, 1H, S(O)CH2); 4.35 (d, 1H, S(O)CH2); 4.72 (qd, 1H, CH2CF3); 4.76 (qd, 1H, CH2CF3); 7.88 (s, 1H, thiazolyl-H).

The retention times (Rt, in minutes) of selected compounds of Tables 1-4 of chiral compounds were determined by analytical chiral HPLC [Chiralcel OD column (250×4.6 mm, particle size 5 μm), temperature 25° C., flow rate 0.6 ml/min, hexane/2-propanol 90:10 v/v or Chiralpak IC column, (250×4.6 mm, particle size 5 μm), temperature 25° C., flow rate 0.6 ml/min, hexane/2-propanol 90:10 v/v; if the solvent ratio is different, this is stated in the text.

NMR data were measured at 400 MHz and in the solvent CDCl3. The chemical shift δ is stated in ppm (TMS reference).

B. FORMULATION EXAMPLES

  • a) A dust is obtained by mixing 10 parts by weight of a compound of the formula (I) and 90 parts by weight of talc as inert substance and comminuting the mixture in a hammer mill.
  • b) A wettable powder which is readily dispersible in water is obtained by mixing 25 parts by weight of a compound of the formula (I), 64 parts by weight of kaolin-containing quartz as inert substance, 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleoylmethyltaurate as wetting agent and dispersant, and grinding the mixture in a pinned-disk mill.
  • c) A readily water-dispersible dispersion concentrate is obtained by mixing 20 parts by weight of a compound of the formula (I) with 6 parts by weight of alkylphenol polyglycol ether (®Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range for example about 255 to above 277° C.) and grinding the mixture in a ball mill to a fineness of below 5 microns.
  • d) An emulsifiable concentrate is obtained from 15 parts by weight of a compound of the formula (I), 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxethylated nonylphenol as emulsifier.
  • e) Water-dispersible granules are obtained by mixing

75 parts by weight of a compound of the formula (I), 10 ″ of calcium lignosulfonate,  5 ″ of sodium lauryl sulfate,  3 ″ of polyvinyl alcohol and  7 ″ kaolin
    • grinding the mixture in a pinned-disk mill, and granulating the powder in a fluidized bed by spraying on water as granulating liquid.
  • f) Water-dispersible granules are also obtained by homogenizing and precomminuting

25 parts by weight of a compound of the formula (I),  5 ″ of sodium 2,2′-dinaphthylmethane-6,6′-disulfonate,  2 ″ of sodium oleoylmethyltaurate,  1 part by weight of polyvinyl alcohol, 17 parts by weight calcium carbonate and 50 ″ of water
    • in a colloid mill, then grinding the mixture in a bead mill, and atomizing and drying the resulting suspension in a spray tower, using a single-fluid nozzle.

C. BIOLOGICAL EXAMPLES

1. Pre-Emergence Herbicidal Effect And Crop Plant Compatibility

Seeds of monocotyledonous or dicotyledonous weed plants or crop plants are placed in sandy loam in wood-fiber pots and covered with soil. The compounds according to the invention, formulated in the form of wettable powders (WP), are then applied as aqueous suspension at a water application rate of 600 l/ha (converted) with the addition of 0.2% of wetting agent to the surface of the covering soil.

After the treatment, the pots are placed in a greenhouse and kept under good growth conditions for the test plants. After about 3 weeks, the effect of the preparations is scored visually in comparison with untreated controls (herbicidal effect in percent (%): 100% activity=the plants have died, 0% activity=like control plants).

As shown by the results, the compounds according to the invention have good herbicidal pre-emergence activity against a broad spectrum of weed grasses and broad-leaved weeds. The compounds Nos. 185, 259, 270, 2555, 2632, 2637, 2719, 1375, 1449, 1460, 3643, 3720, 3725, 2640, 3728 and other compounds from Tables 1-4, for example, have very good herbicidal activity against harmful plants such as, for example, Avena fatua, Stellaria media, Echinochloa crus galli, Lolium multiflorum, Setaria viridis, Abutilon theophrasti, Amaranthus retroflexus, Viola tricolor, Veronica persica and Alopecurus myosuroides when applied by the pre-emergence method at an application rate of 0.32 kg and less of active substance per hectare.

In addition, some substances also spare monocotyledonous and dicotyledonous crops such as wheat and oilseed rape. Some of the compounds according to the invention have high selectivity and are therefore suitable for controlling unwanted vegetation in agricultural crops by the pre-emergence method.

The following results were achieved with the compounds of the formula (Ia) by the pre-emergence method:

according to the Compound invention TRZAS ECHCG LOLMU SETVI VIOTR 185 80 g of 10 100 90 100 70 (S config.) active com- pound/ha 20 g of 0 90 70 70 60 active com- pound/ha Racemate 80 g of 50 90 40 80 0 of 185 active com- (S config.) pound/ha and 1375 20 g of 50 50 40 30 0 (R config.) active com- pound/ha 1375 80 g of 0 80 60 20 80 (R config.) active com- pound/ha 20 g of 0 0 0 0 60 active com- pound/ha

From the above table, it can be deduced that the (S) and (R) stereoisomers of the compounds of the formula (Ia) according to the invention have better herbicidal action against the weed grasses examined than the racemic mixture. At the same time, the crop plant compatibility of the (S) and (R) stereoisomers in wheat is surprisingly high. In particular the simultaneous effect of an enhanced activity against weed grasses and better compatibility with specific crops of the individual stereoisomers was unexpected based on the prior art.

The following results were achieved with the compounds of the formula (Ib) by the pre-emergence method:

according to the Compound invention BRSNW ALOMY LOLMU SETVI 2637 80 g of 0 90 100 90 (S config.) active com- pound/ha 20 g of 0 60 10 80 active com- pound/ha Racemate 80 g of 0 90 80 80 of 2637 active com- (S config.) pound/ha and 3725 20 g of 0 30 0 0 (R config.) active com- pound/ha 3725 80 g of 0 20 0 0 (R config.) active com- pound/ha 20 g of 0 0 0 0 active com- pound/ha

From the above table, it can be deduced that the (S) stereoisomers of the compounds of the formula (I) according to the invention have better herbicidal action against the weed grasses examined than the racemic mixture. At the same time, the crop plant compatibility of the (S) stereoisomers in oilseed rape is surprisingly high, i.e. at increased activity a higher selectivity is achieved, too.

The following results were achieved with the compounds of the formula (Ib) by the post-emergence method:

according to the Compound invention ZEAMX AVEFA LOLMU SETVI POLCO STEME 2640 80 g of 0 90 100 100 100 90 (S config.) active com- pound/ha 20 g of 0 20 60 100 20 10 active com- pound/ha Racemate 80 g of 0 70 80 100 80 20 of 2640 active com- (S config.) pound/ha and 3728 20 g of 0 20 0 20 0 10 (R config.) active com- pound/ha 3728 80 g of 0 10 0 10 10 10 (R config.) active com- pound/ha 20 g of 0 0 0 10 — 0 active com- pound/ha

From the above table, it can be deduced that the (S) stereoisomers of the compounds of the formula (I) according to the invention have better herbicidal action against the weed grasses examined than the racemic mixture. At the same time, the crop plant compatibility of the (S) stereoisomers in oilseed rape is surprisingly high, i.e. at increased activity a higher selectivity is achieved, too.

Abbreviations

  • ZEAMX: Zea mays (corn)
  • TRZAS: Triticum aestivum (summer wheat)
  • ALOMY: Alopecurus myosuroides (black-grass)
  • LOLMU: Lolium multiflorum (Italian ryegrass)
  • SETVI: Setaria viridis (green foxtail)
  • BRSNW: Brassica napus (winter rape)
  • VIOTR: Viola tricolor (wild pansy)
  • ECHCG: Echinochloa crus-galli (barnyard grass)
  • AVEFA: Avena fatua
  • POLCO: Polygunum convolvulus
  • STEME: Stellaria media
    2. Post-Emergence Herbicidal Effect and Crop Plant Compatibility

Seeds of monocotyledonous and dicotyledonous weed and crop plants are placed in sandy loam in wood fibre pots, covered with soil and cultivated in a greenhouse under good growth conditions. 2 to 3 weeks after sowing, the test plants are treated at the one-leaf stage. The compounds according to the invention, formulated in the form of wettable powders (WP), are then applied as aqueous suspension at a water application rate of 600 l/ha (converted) with the addition of 0.2% of wetting agent to the green parts of the plants. After the test plants have been kept in the greenhouse under optimum growth conditions for about 3 weeks, the activity of the preparations is rated visually in comparison to untreated controls (herbicidal activity in percent (%): 100% activity=the plants have died, 0% activity=like control plants).

As shown by the results, the compounds according to the invention have good herbicidal post-emergence activity against a plurality of weed grasses and broad-leaved weeds. The compounds Nos. 185, 259, 270, 2555, 2632, 2637, 2719, 1375, 1449, 3643, 3720, 3725, 2640, 3728 and other compounds from Tables 1-4, for example, have very good herbicidal activity against harmful plants such as, for example, Avena fatua, Echinochloa crus galli, Lolium multiflorum, Setaria viridis and Alopecurus myosuroides when applied by the post-emergence method at an application rate of 0.32 kg and less of active substance per hectare.

In addition, some substances also spare graminaceous and dicotyledonous crops such as corn and oilseed rape. Some of the compounds according to the invention have high selectivity and are therefore suitable for controlling unwanted vegetation in agricultural crops by the post-emergence method.

Claims

1. An optically active compound of formula (I) in the (S) configuration and/or an agrochemically acceptable salt and/or an agrochemically acceptable quaternized nitrogen derivative thereof wherein and

Y is
the substituents R1 to R5 are each independently of one another selected from the group consisting of
hydrogen, halogen, hydroxyl, cyano, nitro, amino, C(O)OH, formyl,
(C1-C6)-alkyl, (C1-C6)-haloalkyl, (C1-C6)-alkylcarbonyl, (C1-C6)-haloalkylcarbonyl, (C1-C6)-alkylcarbonyloxy, (C1-C6)-haloalkylcarbonyloxy, (C1-C6)-alkylcarbonyl-(C1-C4)-alkyl, (C1-C6)-haloalkylcarbonyl-(C1-C4)-alkyl, (C1-C6)-alkylcarbonyl-(C1-C4)-haloalkyl, (C1-C6)-haloalkylcarbonyl-(C1-C4)-haloalkyl,
(C1-C6)-alkoxy, (C1-C6)-haloalkoxy, (C1-C6)-alkoxycarbonyl, (C1-C6)-haloalkoxycarbonyl, (C1-C6)-alkoxycarbonyl-(C1-C6)-alkyl, (C1-C6)-haloalkoxycarbonyl-(C1-C6)-alkyl, (C1-C6)-alkoxycarbonyl-(C1-C6)-haloalkyl, (C1-C6)-haloalkoxycarbonyl-(C1-C6)-haloalkyl,
(C2-C6)-alkenyl, (C2-C6)-haloalkenyl, (C2-C6)-alkenylcarbonyl, (C2-C6)-haloalkenylcarbonyl, (C2-C6)-alkenyloxy, (C2-C6)-haloalkenyloxy, (C2-C6)-alkenyloxycarbonyl, (C2-C6)-haloalkenyloxycarbonyl,
(C2-C6)-alkynyl, (C2-C6)-haloalkynyl, (C2-C6)-alkynylcarbonyl, (C2-C6)-haloalkynylcarbonyl, (C2-C6)-alkynyloxy, (C2-C6)-haloalkynyloxy, (C2-C6)-alkynyloxycarbonyl, (C2-C6)-haloalkynyloxycarbonyl,
(C1-C6)-alkylthiocarbonyl, (C1-C6)-haloalkylthiocarbonyl, (C 1-C6)-alkylthiocarbonyloxy, (C1-C6)-haloalkylthiocarbonyloxy,
(C1-C6)-alkylthio-(C1-C6)-alkoxy, (C1-C6)-alkylthio-(C1-C6)-alkylcarbonyl, (C1-C6)-alkylthio-(C1-C6)-alkylcarbonyloxy,
(C6-C14)-aryl, (C6-C14)-aryloxy, (C6-C14)-arylcarbonyl, (C6-C14)-aryloxycarbonyl,
(C6-C14)-aryl-(C1-C6)-alkyl, (C6-C14)-aryl-(C1-C6)-alkoxy, (C6-C14)-aryloxy-(C1-C6)-alkyl, (C6-C14)-aryl-(C1-C6)-alkyl-carbonyl, (C6-C14)-aryl-(C1-C6)-alkyl-carbonyloxy, (C6-C14)-aryl-(C1-C6)-alkoxycarbonyl, (C6-C14)-aryl-(C1-C6)-alkoxycarbonyloxy,
(C1-C6)-alkylsulfonyl, (C1-C6)-alkylthio, (C1-C6)-alkylsulfinyl, (C1-C6)-halo-alkylsulfonyl, (C1-C6)-haloalkylthio, (C1-C6)-haloalkylsulfinyl, (C1-C6)-alkylsulfonyl-(C1-C6)-alkyl, (C1-C6)-alkylthio-(C1-C6)-alkyl, (C1-C6)-alkylsulfinyl-(C1-C6)-alkyl, (C1-C6)-haloalkylsulfonyl-(C1-C6)-alkyl, (C1-C6)-haloalkylthio-(C1-C6)-alkyl, (C1-C6)-haloalkylsulfinyl-(C1-C6)-alkyl, (C1-C6)-alkylsulfonyl-(C1-C6)-haloalkyl, (C1-C6)-alkylthio-(C1-C6)-haloalkyl, (C1-C6)-alkylsulfinyl-(C1-C6)-haloalkyl, (C1-C6)-haloalkylsulfonyl-(C1-C6)-haloalkyl, (C1-C6)-haloalkylthio-(C1-C6)-haloalkyl, (C1-C6)-haloalkylsulfinyl-(C1-C6)-haloalkyl, (C1-C6)-alkylsulfonyloxy, (C1-C6)-haloalkylsulfonyloxy,
(C4-C14)-arylsulfonyl, (C6-C14)-arylthio, (C6-C14)-arylsulfinyl,
mono-((C1-C6)-alkyl)-amino, mono-((C1-C6)-haloalkyl)-amino, di-((C1-C6)-alkyl)-amino, di-((C1-C6)-haloalkyl)-amino, ((C1-C6)-alkyl-(C1-C6)-haloalkyl)-amino, N—((C1-C6)-alkanoyl)-amino, N—((C1-C6)-haloalkanoyl)-amino, aminocarbonyl-(C1-C6)-alkyl, mono-(C1-C6)-alkylaminocarbonyl-(C1-C6)-alkyl, di-(C1-C6)-alkylaminocarbonyl-(C1-C6)-alkyl, mono-((C1-C6)-alkyl)-aminocarbonyl,
(C1-C6)-alkoxy-(C1-C6)-alkyl, (C1-C6)-alkoxy-(C1-C6)-alkoxy, (C1-C6)-alkoxy-carbonyl-(C1-C6)-alkoxy,
(C3-C8)-cycloalkyl, (C3-C8)-cycloalkoxy, (C3-C8)-cycloalkyl-(C1-C6)-alkyl, (C3-C8)-cycloalkyl-(C1-C6)-haloalkyl, (C3-C8)-cycloalkyl-(C1-C6)-alkoxy, (C3-C8)-cycloalkyl-(C1-C6)-haloalkoxy, (C3-C8)-cycloalkylcarbonyl, (C3-C8)-cycloalkoxycarbonyl, (C3-C8)-cycloalkyl-(C1-C6)-alkylcarbonyl, (C3-C8)-cycloalkyl-(C1-C6)-haloalkylcarbonyl, (C3-C8)-cycloalkyl-(C1-C6)-alkoxycarbonyl, (C3-C8)-cycloalkyl-(C1-C6)-haloalkoxycarbonyl, (C3-C8)-cycloalkylcarbonyloxy, (C3-C8)-cycloalkoxycarbonyloxy, (C3-C8)-cycloalkyl-(C1-C6)-alkylcarbonyloxy, (C3-C8)-cycloalkyl-(C1-C6)-haloalkylcarbonyloxy, (C3-C8)-cycloalkyl-(C1-C6)-alkoxycarbonyloxy, (C3-C8)-cycloalkyl-(C1-C6) -haloalkoxycarbonyloxy,
(C3-C8)-cycloalkenyl, (C3-C8)-cycloalkenyloxy, (C3-C8)-cycloalkenyl-(C1-C6)-alkyl, (C3-C8)-cycloalkenyl-(C1-C6)-haloalkyl, (C3-C8)-cycloalkenyl-(C1-C6)-alkoxy, (C3-C8)-cycloalkenyl-(C1-C6)-haloalkoxy, (C3-C8)-cycloalkenylcarbonyl, (C3-C8)-cycloalkenyloxycarbonyl, (C3-C8)-cycloalkenyl-(C1-C6)-alkylcarbonyl, (C3-C8)-cycloalkenyl-(C1-C6)-haloalkylcarbonyl, (C3-C8)-cycloalkenyl-(C1-C6)-alkoxycarbonyl, (C3-C8)-cycloalkenyl-(C1-C6)-haloalkoxycarbonyl, (C3-C8)-cycloalkenylcarbonyloxy, (C3-C8)-cycloalkenyloxycarbonyloxy, (C3-C8)-cycloalkenyl-(C1-C6)-alkylcarbonyloxy, (C3-C8)-cycloalkenyl-(C1-C6)-haloalkylcarbonyloxy, (C3-C8)-cycloalkenyl-(C1-C6)-alkoxycarbonyloxy, (C3-C8)-cycloalkenyl-(C1-C6)-haloalkoxycarbonyloxy,
(C3-C8)-cycloalkylthio, (C3-C8)-alkenylthio, (C3-C8)-cycloalkenylthio, (C3-C6)-alkynylthio,
hydroxy-(C1-C6)-alkyl, hydroxy-(C1-C6)-alkoxy, cyano-(C1-C6)-alkoxy, cyano-(C1-C6)-alkyl,
3-oxetanyloxy, and
C(O)NR9R10 where R9 and R10 independently of one another are hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C1-C6)-haloalkyl, or where R9 and R10together form a (C1-C6)-alkylene group which may contain one oxygen or sulfur atom or one or two amino or (C1-C6)-alkylamino groups,
where the R1 to R5 substituents may, if appropriate, be attached cyclically to one another, provided they are ortho to one another
and/or two of the R1 to R5 substituents ortho to one another together form a (C1-C6)-alkylene group which may contain one or more oxygen and/or sulfur atoms, where the (C1-C6)-alkylene group may be mono- or polysubstituted by halogen and the halogen substituents in question may be identical or different;
where the radicals R1 to R5 mentioned above may be mono- or polysubstituted independently of one another by at least one radicals selected from the group consisting of (C1-C6)-alkyl, (C1-C6)-alkoxy, nitro, cyano, (C1-C3)-cycloalkyl, (C1-C6)-haloalkoxy, and (C1-C6)-alkylthio and halogen, where the radicals mentioned may optionally be cyclically attached to one another, provided they are ortho to each other; and
the substituents R11 and R12, in each case independently of one another, are selected from the group consisting of
hydrogen, halogen, nitro, cyano, formyl, C(O)OH, hydroxyl, amino,
(C1-C6)-alkyl, (C1-C6)-alkylcarbonyl, (C1-C6)-alkylcarbonyl-(C1-C4)-alkyl, (C1-C6)-alkylcarbonyloxy,
(C1-C6)-alkoxy, (C1-C6)-alkoxycarbonyl, (C1-C6)-alkoxycarbonyl-(C1-C6)-alkyl, (C1-C6)-alkoxy-(C1-C6)-alkyl, (C1-C6)-alkoxy-(C1-C6)-alkoxy, (C1-C6)-alkoxycarbonyl-(C1-C6)-alkoxy,
(C2-C6)-alkenyl, (C2-C6)-alkenyloxy, (C2-C6)-alkynyl, (C2-C6)-alkynyloxy,
(C1-C6)-alkylthio, (C1-C6)-alkylsulfinyl, (C1-C6)-alkylsulfonyl, (C1-C6)-alkylsulfonyloxy, (C1-C6)-alkylsulfonyl-(C1-C6)-alkyl, (C1-C6)-alkylsulfinyl-(C1-C6)-alkyl, (C1-C6)-alkylthio-(C1-C6)-alkyl, (C1-C6)-alkylthio-(C1-C6)-alkoxy,
mono-((C1-C6)-alkyl)-amino, di-((C1-C6)-alkyl)-amino, N—((C1-C6)-alkanoyl)-amino, aminocarbonyl-(C1-C6)-alkyl, mono-((C1-C6)-alkyl)-aminocarbonyl, di-((C1-C6)-alkyl)-aminocarbonyl, mono-((C1-C6)-alkyl)-aminosulfonyl, di-((C1-C6)-alkyl)-aminosulfonyl,
(C3-C8)-cycloalkyl, (C3-C8)-cycloalkoxy, (C3-C8)-cycloalkyl-(C1-C6)-alkyl, (C3-C8)-cycloalkyl-(C1-C6)-alkoxy, (C3-C8)-cycloalkylcarbonyl, (C3-C8)-cycloalkoxycarbonyl,
(C3-C8)-cycloalkenyl, (C3-C8)-cycloalkenyloxy, (C3-C8)-cycloalkylthio, (C3-C8)-cycloalkylsulfinyl, (C3-C8)-cycloalkylsulfonyl, (C3-C8)-cycloalkylsulfonyloxy,
cyano-(C1-C6)-alkoxy, cyano-(C1-C6)-alkyl,
(C6-C14)-aryl, (C6-C14)-aryloxy, (C6-C14)-aryl-(C1-C6)-alkyl, (C6-C14)-aryl-(C1-C6)-alkoxy, (C6-C14)-aryloxy-(C1-C6)-alkyl,
—CONH—SO2—(C1-C6)-alkyl, —NHCHO, —NHCO—(C1-C6)-alkyl, —NHCO2—(C1-C6)-alkyl, —NHCONH—(C1-C6)-alkyl, —NHSO2—(C1-C6)-alkyl, —OCONH—(C1-C6)-alkyl, (C1-C6)-alkylaminosulfonyl-(C1-C2)-alkyl, di-(C1-C6)-alkylaminosulfonyl-(C1-C2)-alkyl, —C(O)NHR9, and
—C(O)NR9R10 where R9 and R10 independently of one another are hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C1-C6)-haloalkyl, or where R9 and R10 together form a (C1-C6)-alkylene group which may contain one oxygen or sulfur atom or one or two amino or (C1-C6)-alkylamino groups,
where the radicals R11 and R12 mentioned above may be mono- or polysubstituted independently of one another by radicals selected from the group consisting of halogen and (C1-C6)-alkyl.

2. The compound of the formula (I) as claimed in claim 1 wherein Y is and the substituents R1 to R5 independently of one another are selected from the group consisting of hydrogen, hydroxyl, halogen, cyano, nitro, amino, C(O)OH, (C1-C4)-alkyl, (C3-C6)-cycloalkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, (C1-C4)-alkoxy-(C1-C2)-alkyl, (C1-C3)-alkylcarbonyl, (C1-C3)-alkylcarbonyloxy, (C1-C4)-alkoxycarbonyl, (C3-C6)-cycloalkoxycarbonyl, (C3-C6)-cycloalkyl-(C1-C2)-alkoxy, (C3-C6)-cycloalkoxy, (C1-C4)-alkoxycarbonyl-(C1-C2)-alkoxy, (C3-C4)-alkenyloxy, (C3-C4)-alkynyloxy, (C1-C4)-alkylthio, (C1-C4)-haloalkylthio, (C1-C4)-alkylsulfinyl, (C1-C4)-haloalkylsulfinyl, (C1-C4)-alkylsulfonyl, (C1-C4)-haloalkylsulfonyl, (C1-C4)-alkylsulfonyloxy, di-(C1-C4)-alkylamino, C6-aryl-(C1-C4)-alkyl, (C3-C4)-alkenyloxycarbonyl, (C2-C4)-alkynyloxycarbonyl, C6-aryl-(C1-C4)-alkoxycarbonyl, C6-aryl-(C1-C4)-alkoxy, formyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, phenyl, and —C(O)NR9R10, where R9 and R10 independently of one another are selected from the group consisting of hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, and (C1-C6)-haloalkyl, or where R9 and R10 together form a (C1-C6)-alkylene group which may contain one oxygen or sulfur atom or one or two amino or (C1-C6)-alkylamino groups.

3. The compound of the formula (I) as claimed in claim 1 wherein R11 and R12 independently of one another are selected from the group consisting of hydrogen, halogen, nitro, cyano, carboxyl, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C3-C6)-cycloalkoxy, (C1-C6)-alkoxy, (C1-C6)-alkylcarbonyl, (C3-C6)-cycloalkylcarbonyl, (C1-C6)-alkoxycarbonyl, (C3-C6)-cycloalkoxycarbonyl, mono-((C1-C4)-alkyl)-aminocarbonyl, di-((C1-C4)-alkyl)-aminocarbonyl, mono-((C1-C4)-alkyl)-aminosulfonyl, di-((C1-C4)-alkyl)-aminosulfonyl, (C1-C4)-alkylthio, (C3-C6)-cycloalkylthio, (C1-C4)-alkylsulfinyl, (C3-C6)-cycloalkylsulfinyl, (C1-C4)-alkylsulfonyl, (C3-C6)-cycloalkylsulfonyl, (C1-C4)-alkylsulfonyloxy, (C3-C6)-cycloalkylsulfonyloxy, (C2-C3)-alkenyl, (C2-C3)-alkynyl, (C2-C3)-alkenyloxy, (C2-C3)-alkynyloxy, —NHCO—(C1-C3)-alkyl, —NHCO2—(C1-C3)-alkyl, —NHCONH—(C1-C3)-alkyl, —NHSO2—(C1-C3)-alkyl, —OCONH—(C1-C3)-alkyl, —CONHR9, and —CONR9R10, where R9 and R10 independently of one another are hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, or (C1-C6)-haloalkyl, where the radicals R11 and R12 mentioned above may be mono- or polysubstituted independently of one another by radicals selected from the group consisting of halogen and (C1-C6)-alkyl.

4. The compound of the formula (I) as claimed in claim 1 wherein R11 and R12 independently of one another are selected from the group consisting of H, F, Cl, Br, I, Me, CHF2 and CF3.

5. The compound of the formula (I) as claimed in claims 1 wherein R11 and R12 independently of one another are selected from the group consisting of F, Cl, Br and I.

6. The compound according to claim 1 in which Y is and the radicals R1 to R5 and R11 and R12 have the meanings according to claim 1, except for the compounds 2-(benzylsulfinyl)-1,3-thiazole, 2-(benzylsulfinyl)-5-(chloromethyl)-1,3-thiazole, 5-(chloromethyl)-2-(4-methylbenzyl)sulfinyl-1,3-thiazole, 5-(chloromethyl)-2-(4-methoxybenzyl)sulfinyl-1,3-thiazole, 2-(4-chlorobenzyl)sulfinyl-5-(chloromethyl)-1,3-thiazole, 5-(chloromethyl)-2-(4-nitrobenzyl)sulfinyl-1,3-thiazole, 5-(bromomethyl)-2-(4-nitrobenzyl)sulfinyl-1,3-thiazole, 5-(bromomethyl)-2-(4-chlorobenzyl)sulfinyl-1,3-thiazole, 5-(bromomethyl)-2-(4-methoxybenzyl)sulfinyl-1,3-thiazole, 5-(bromomethyl)-2-(4-methylbenzyl)sulfinyl-1,3-thiazole and 2-(benzylsulfinyl)-5-(bromomethyl)-1,3-thiazole.

7. A process for preparing a compound of the formula (I) as claimed in claim 1, which comprises oxidizing a thioether of the formula (II) with one equivalent of an oxidizing agent to give a sulfoxide of the formula (I)

8. The process as claimed in claim 7 wherein the oxidizing agent is selected from the group consisting of hydrogen peroxide, sodium metaperiodate, organic peroxides and organic peracids.

9. A composition comprising at least one compound of the formula (I) as claimed in claim 1.

10. The composition as claimed in claim 9 wherein the composition comprises at least one further active compound selected from the group consisting of at least one further herbicide and at least one safener.

11. A plant growth regulator comprising a compound of the formula (I) as claimed in claim 1.

12. A plant growth regulator comprising a composition as claimed in claim 9.

13. A method for controlling plants in specific plant crops comprising applying plant protection regulator of claim 9 to said crops.

14. The compound of the formula (I) as claimed in claim 1 wherein R1, R5 and R11 are halogen and R2, R3, R4 and R12 are hydrogen, and Y is phenyl.

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Patent History
Patent number: 8754234
Type: Grant
Filed: Nov 8, 2008
Date of Patent: Jun 17, 2014
Patent Publication Number: 20100285958
Assignee: Bayer Cropscience AG (Monheim)
Inventors: Hansjörg Dietrich (Liederbach am Taunus), Arianna Martelletti (Sulzbach), Christopher Hugh Rosinger (Hofheim), Jan Dittgen (Frankfurt), Dieter Feucht (Eschborn)
Primary Examiner: Nyeemah A Grazier
Application Number: 12/743,862
Classifications
Current U.S. Class: Chalcogen Attached Indirectly To The Thiazole Ring By Nonionic Bonding (548/186); Chalcogen Bonded Directly To Ring Carbon Of The Thiazole Ring (514/369)
International Classification: C07D 277/00 (20060101); A61K 31/425 (20060101);